Synthesis and solid state characterization of actinide cyanometallates and 
actinide benzimidazole compounds  
 
by 
 
Branson A. Maynard 
 
 
 
 
A disertation submited to the Graduate Faculty of 
Auburn University 
in partial fulfilment of the 
requirements for the Degree of 
Doctor of Philosophy  
 
Auburn, Alabama 
May 4, 2014 
 
 
 
 
 
 
Copyright 2014 by Branson Alen Maynard 
 
 
Approved by 
 
Anne Gorden, Chair, Asociate Profesor, Department of Chemistry and Biochemistry 
David Stanbury, J. Milton Harris Profesor, Department of Chemistry and Biochemistry 
Michael McKe, Profesor, Department of Chemistry and Biochemistry 
Curtis Shannon, Andrew T. Hunt Profesor, Department of Chemistry and Biochemistry 
 
 
 
 
 
 
ii 
 
 
 
 
 
 
 
 
 
 
 
 
Abstract 
 
 
 The square-planar cyanometalate anions alow for the unique columnar structural feature 
in the solid state, termed in the literature as pseudo 1-D M
?
M interactions in the Pt analogs. The 
distance betwen metal sites has been coined, R, and can be tuned by many physical and 
chemical proceses. While the akali and alkaline earth metal tetracyanoplatinates have been 
known for two centuries, few compounds have been reported in the actinide square planar 
cyanometalate clas of compounds, An
x
[M(CN)
4
]
y
. Utilizing this structural feature provides a 
new means for probing the chemistry of the 5f elements. Described here is the synthesis, 
emision spectroscopy, Raman spectroscopy, computation analysis, and structural 
characterization using smal molecule X-ray single crystal difraction of the recently reported 
actinide cyanometalates, general formula An
x
[M(CN)
4
]
y
. 
 
 
 
 
 
 
 
 
 
 
 
 
 iii 
 
 
 
 
 
 
 
 
 
 
 
Acknowledgements 
 
 
 First, I wil make the acknowledgement that I wil forget to mention someone, or funding 
agency, that has provided support for this work. My parents, Mark and Sharon, played the 
principal role in facilitating an environment where pursuit of higher education was important.  
Along these lines, the research I performed under the supervision of Dr. Richard Sykora at the 
University of South Alabama was paramount to starting a path in structural elucidation of solid 
state f-block coordination compounds. 
 Further, I have been lucky enough to receive several outside funding sources that 
provided learning opportunities that were not possible on the campus of Auburn University.  
These include a trip to Oak Ridge National Laboratory to learn neutron difraction techniques 
(Funding: Oak Ridge National Laboratory and Argonne National Laboratory) and a summer 
felowship to Los Alamos National Laboratory to learn computational analysis (Funding: 
Seaborg Institute).  Also the local section of the American Chemical Society and the Auburn 
University Graduate School have provided funding to diseminate my research at local and 
national metings.   Research asistance has been provided through DTRA.  
 Certainly other names should be included as during one point or another of this graduate 
study I received valuable insight into a problem:  John Gorden, Mohan Bharara, Brian Litle, 
 iv 
Kushan Weirasairi, Mike Devore, Walter Casper, Nick Klann, Phong Ngo and the many other 
graduate and undergraduate students. 
Undoubtedly I would be remis if I did not acknowledge Dr. Anne Gorden.  During my 
time at Auburn University she has provided advice, leadership, and mentoring in the proper 
doses.  I wil be forever grateful that Dr. Gorden was my primary investigator.  Additionaly I 
would like to thank Dr. Gorden and Dr. Ortiz for continuing my funding during the time I was in 
the hospital and recovering.  Also I would like to thank my commite members for proofreading 
this text. 
Last but, certainly not least; I wil forever be indebted to my wife, Amanda Maynard, for 
her support through the toughest times of this doctoral work. The reason why this text exists is, 
in large part, due to her understanding that it may not ever be writen, or I would not be able to 
write it.  Amanda provided this understanding at the time I needed it most and it helped serve as 
motivation to make sure it was writen.       
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 v 
 
 
 
 
 
 
 
 
 
 
 
 
Table of Contents 
 
 
Abstract ......................................................................................................................................... ii 
Acknowledgments ........................................................................................................................ iii 
List of Tables .............................................................................................................................. vi 
List of Illustrations ..................................................................................................................... vii 
List of Abbreviations ................................................................................................................... xi 
Chapter 1 Introduction   ................................................................................................................ 1 
 A Brief History of a 5f Element, Uranium ........................................................................ 1 
 5f Coordination Compounds ............................................................................................ 6 
 References Cited ............................................................................................................ 24 
Chapter 2 Solid State Structural Elucidation of the Th
IV
, UO
2
VI
, and U
IV
 Cyanometalates ..... 27 
 5f-Cyanometalate Coordination Complexes .................................................................. 33 
 Crystalographic Overview ............................................................................................. 53 
 References Cited ............................................................................................................. 56 
Chapter 3 Emision and Raman Spectroscopy of the Actinide Tetracyanometalates .............. 59 
 Excitation and Emision ................................................................................................. 60 
 Raman Spectroscopy ....................................................................................................... 66 
 vi 
 DFT analysis ................................................................................................................... 71 
 Discussion ....................................................................................................................... 74 
 Conclusions ..................................................................................................................... 80 
 References Cited ............................................................................................................. 86 
Chapter 4 Synergistic Thorium Mediated Synthesis of 2,3-Diaminophenazine ......................... 89 
 Conclusions ..................................................................................................................... 94 
 References Cited ............................................................................................................. 98 
Chapter 5 Synthesis, Isolation, Structural Characterization and Emision Spectroscopy of Salzine 
            Compounds ..................................................................................................................... 99 
 X-ray difraction ........................................................................................................... 102 
 CRAIC Microspectrophotometer .................................................................................. 105 
 References Cited ........................................................................................................... 110 
Chapter 6 Conclusions and Future Work .................................................................................. 111 
 Future Work .................................................................................................................. 112 
Appendix 1: Crystalographic Tables   ..................................................................................... 119 
 
 
 
 
 
 
 
 
 vii 
 
 
 
 
 
 
 
 
 
 
 
List of Tables 
 
 
Table 1 ORTEP projections of solid state actinide complexed ligands ........................................ 5 
Table 2 Crystalographic information for Th1, Th2, and U3 ...................................................... 50 
Table 3 Crystalographic information for U4, Th5, and U6 ....................................................... 51 
Table 4 Crystalographic information for Th7 and Th8 .............................................................. 52 
Table 5 Cyanide vibrational stretches of the cyanometalate salts ............................................. 67 
Table 6 Single point energy calculations performed .................................................................. 72 
Table 7 Cyanide vibrational stretches of Th1, Th2, U3, U4, Th5, and U6 ................................. 76 
Table 8 Vibrational modes calculated by the unrestricted B3LYP functional ........................... 80 
Table 9 Tabulated results from the oxidation of OPD ................................................................ 96 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 vii 
 
 
 
 
 
 
 
 
 
 
 
 
List of Illustrations 
 
 
Figure 1 Thermal elipsoid projection of [UO
2
 (N,N-bis(2-hydroxy-3,5-dimethylbenzyl)-4- 
             amino-1-butanol)] ............................................................................................................ 6 
 
Figure 2 Thermal elipsoid projection of [UO
2
(N?,N?-bis(2-hydroxy-3-methoxy-5-(propen-2- 
              yl)benzyl-N-(2-aminoethyl)morpholine)
2
]?2CH
3
CN ..................................................... 8 
 
Figure 3 Thermal elipsoid projection of {UO
2
(?
2
-ReO
4
)(ReO
4
)(TBPO)
2
]
2
 ............................... 9 
Figure 4 Thermal elipsoid projection of [UO
2
(3-(2-Hydroxybenzylideneamino)propane-1,2- 
               diol)]
2
?C
3
H
7
NO ........................................................................................................... 11 
 
Figure 5 Thermal elipsoid projection of UO
2
(2-quinoxilinol) .................................................. 12 
Figure 6 Thermal elipsoid projection of [Cyclo[6]pyrrole (UO
2
)] ........................................... 15 
Figure 7 The bal and stick projection of [NpO
2
([18]crown-6)]
+
 .............................................. 17 
Figure 8 Projection of [Pu(5LIO(Me-3,2-HOPO)
2
)] .................................................................. 19 
Figure 9 Projection of PuI
2
(
Ar
acnac)
2
 ......................................................................................... 22 
Figure 10 Asymmetric unit of Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O (Th1)   ........................................... 33 
Figure 11 Packing diagram of Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O (Th1)   .......................................... 34 
Figure 12 Projection of Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O (Th2)  ........................................... 35 
Figure 13 Packing diagram of Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O (Th2) .................................. 36 
Figure 14 Packing diagram of K
3
[(UO
2
)
2
(OH)(Pt(CN)
4
)
2
]
2
?NO
3
?1.5H
2
O (U3) ........................ 37 
 ix 
Figure 15 Projection of {U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O (U3)  .............................................. 40 
Figure 16 Packing diagram of {U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O  (U4)  ................................... 42 
Figure 17 Projection of {Th
2
(H
2
O)
10
(OH)
2
[Pd(CN)
4
]
3
}?8H
2
O (Th5) ........................................ 43 
Figure 18 Extension of the one-dimensional structure of 
                         {(UO
2
)
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]} ................................................................... 45 
Figure 19 Projection of the ionic structure of [Th(C
2
H
6
SO)
9
][Pt(CN)
4
]
2
?4H
2
O (Th7) .............. 47 
Figure 20 Projection of the structure of [Th(C
2
H
6
SO)
8
][Fe(CN)
6
]?NO
3
 (Th8) .......................... 48 
Figure 21 Single crystal sample of Th(H
2
O)
7
[Pt(CN)
4
]
2
?H
2
O (TH1) ......................................... 60 
Figure 22 Emision spectra of starting materials, Th1, Th2 and U3 .......................................... 61 
Figure 23 Excitation spectrum of Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O (TH1) ....................................... 63 
Figure 24 Excitation spectrum of Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O (Th2) ............................. 64 
Figure 25 Emision spectra of the K
+
 salts of the d
8
 tetracyanometalates ................................. 65 
Figure 26 Raman spectra of the K
+
 salts of the d
8
 tetracyanometalates .................................... 66 
Figure 27 Raman data of Th1 and Th2 ....................................................................................... 68 
Figure 28 Raman spectra of  Th5 ................................................................................................ 69 
Figure 29 Raman spectrum of U4 ............................................................................................... 70 
Figure 30 Projections of the atom positions from jobs run in Gaussian ..................................... 74 
Scheme 1 Oxidation of ortho-phenylenediamine to 2,3-diaminobenzene .................................. 89 
Figure 31 Scater plot depicting the data from OPD oxidation reactions   ................................. 90 
Figure 32 Projection of the asymmetric unit of (C
12
H
10
N
4
)
2
?7H
2
O ............................................ 93 
Figure 33 Projection of the 2-quinoxolinol salen molecule ........................................................ 99 
Figure 34 Projection of the asymetric unit of the salzine molecule .......................................... 103 
Scheme 2 Proposed reaction scheme for the salzine synthesis. ................................................ 102 
 x 
 
Figure 35 Projection of the asymetric unit of tbut-salzine ........................................................ 103 
Figure 36 Projection of the asymmetric unit of salzine-UO
2
 .................................................... 104 
Figure 37 Transmision and emision spectra of the salzine compound .................................. 105 
Figure 38 Transmision and emision spectra of the salzine-UO
2
 complex ............................. 106 
Figure 39 Transmision and emision spectra of the tbut-salzine ............................................ 107 
Figure 40 Transmision and emision spectra of 2-quinoxalinol salen .................................... 108 
Scheme 3 Reaction of 2,3-diaminophenazine with glycine to form the phenazineimidazole 
                         product ............................................................................................................. 115 
 
Scheme 4 Starting with the phenazineimidazole starting material. .......................................... 116 
Figure 41 Possible 2:1 salzine metal complex. ......................................................................... 117 
Figure 42 Possible 1:1 phenezeneimidazole metal complex. ................................................... 117 
 
 
 
 
 
 
 
 
 xi 
 
 
 
 
 
 
 
 
 
 
List of Abbreviations 
 
 
BTBP Bis-triazinyl bipyridine 
CIF Crystalographic Information file 
Cp Cyclopentadienyl ligand 
CP* Pentamethylcyclopentadienyl ligand 
DAP 2,3-diaminophenazine 
DFE  Desferrioxamine E 
DMA Dimethyacetamide 
DMF Dimethylformamide 
DMSO  Dimethylsulfoxide 
mWe million wats of electric capacity  
OPD ortho-phenylenediamine  
SMMs Single molecule magnets 
TBP Tributyl Phosphate 
TCNi Tetracyanonickelate 
TCPd Tetracyanopaladate 
TCPt Tetracyanoplatinate 
 xii 
TPTZ Tripyridyl triazine 
UV Ultraviolet 
XRD X-ray difraction 
 xii 
 
Reference format follows the format of the Journal of the American Chemical Society 
Crystalographic projections were generated in Olex2.1 
Figures or tables are made by Microsoft Word or Microsoft Excel 
Portions of this disertation are from published articles: 
Chapter 1: Introduction 
Gorden, A. E. V.; DeVore, M. A.; Maynard, B. A. Inorganic Chemistry 2013, 52, 3445. 
Chapter 2 
Maynard, B. A.; Sykora, R. E.; Mague, J. T.; Gorden, A. E. V. Chemical Communications 2010, 
46, 4944. 
 
Maynard, B. A.; Lynn, K. S.; Sykora, R. E.; Gorden, A. E. V. Journal of Radioanalytical and 
Nuclear Chemistry 2013, 296, 453. 
 
Maynard, B. A.; Lynn, K. S.; Sykora, R. E.; Gorden, A. E. V. Inorganic Chemistry 2013, 52, 
4880. 
 
Chapter 3 
 
Maynard, B. A.; Lynn, K. S.; Sykora, R. E.; Gorden, A. E. V. Inorganic Chemistry 2013, 52, 
4880. 
 1 
Chapter 1: Introduction 
 
 
 
The existence of the 5f actinide elements, thorium and uranium, has been known 
for roughly 200 years (185 and 225 years respectively). 
1
  Uranium is important from a 
historical standpoint, as it is one of two elements that stopped World War II by the 
detonation of nuclear fission bombs over the cities of Hiroshima and Nagasaki.  The 
history of uranium is important to mention in the context of how and why it has been 
released into the environment. Following the brief historical recap of uranium is an 
overview of the last decade of actinide-containing solid state structures. This highlights 
the structure-function relationship and the importance of establishing bonding parameters 
in the 5f series.  This leads the way for the main text, which discusses the solid state 
structural elucidation and properties of two new classes of actinide containing 
compounds: actinide cyanometallates and actinide benzimidazoles.  
 
A Brief History of a 5f Element, Uranium 
  
 Martin Heinrich Klaproth is credited to first identifying the element uranium, 
found in a heterogeneous oxide ore commonly known as pitchblende, in 1789.
1
 Enrico 
Fermi first reported the bombarding of uranium with neutrons and incorrectly concluded 
the nuclear absorption of the neutron and subsequent nuclear decay yielded elements with 
93 and 94 protons, essentially claiming the discovery of the elements that would later be 
 2 
named neptunium and plutonium.
2
    Ida Noddack may have been the first, publicly, to 
suggest that the uranium nucleus may break up into several large fragments when 
bombarded by a neutron.
3
  We know this now to be induced nuclear fission, but the term 
fission was only used in reference to the process in cell biology at the time. Her 
description of the process "it is conceivable that the nucleus breaks up into several large 
fragments, which would of course be isotopes of known elements, but would not be 
neighbors of the irradiated element." Otto Frisch and Lise Meitner were both more 
famously credited with discovering fission during an excursion; Frisch was skiing and 
Meitner was walking, and reportedly keeping pace with Frisch, through the countryside.  
Their conversation centered on a letter Otto Hahn had sent Meitner describing that the 
neutron bombardment product of uranium contains barium.   Frisch and Meitner worked 
out the calculations on a fallen tree trunk.  Their idea was that the incoming/bombarding 
neutron perturbed the nucleus enough to produce two large fragments, explaining the 
appearance of barium.
4
 
This is understood more easily, if the nucleus is considered as a liquid drop.  Two 
forces are present; the weak force can be understood as surface tension and the 
electromagnetic force, which is due to the positively charged protons repelling 
themselves.
4
 If the number of neutrons and protons in the nucleus is sufficiently high, 
then the surface tension of the liquid drop is just enough to counterbalance the repulsive 
force of the protons.  If a bombarding neutron finds the liquid drop nucleus of 
235
U, it can 
rupture the liquid drop into two more stable fragments.  The now excess nuclear binding 
energy of the two fragments is released and the amount of energy can be found if the 
 3 
daughter products are known from Einstein?s E=mc
2
.
 
4,5
  From these early observations, it 
could be deduced that large sums of energy could be realized from a fission incident. 
Nowadays, world energy consumption is expected to increase by 47% from 2010 
to 2035.  This increased energy consumption is proportional to the flourishing economies 
outside of the Organisation for Economic Co-operation and Development.
6
 The United 
States used coal to provide over 1,700 billion kilowatt hours of electricity in 2009 alone, 
accounting for almost half of the total electricity produced,
2
 but growing environmental 
concern over the release of greenhouse gases, in particular carbon dioxide from fossil 
fuels, has caused investigation into incorporating the use of other energy sources.
7
 
Nuclear energy can help meet these growing demands and offers energy production in a 
cleaner fashion with lower atmospheric emission. 
  The first full-scale nuclear power plant began operation in 1957 in Shippingport, 
Pennsylvania, marking the United States entry into the civilian nuclear power industry.
4
 
The United States has adopted a once-through fuel cycle, where nuclear fuel rods are 
made from naturally occurring sources and all used nuclear fuel is disposed of after a 
single use. For this type of fuel cycle, enriched uranium fuel or thorium-uranium fuel are 
the only fuels that can be used in order to create a sustainable fission chain reaction 
without a large input of an external neutron source.
7
 
   Today, there are over 400 nuclear power plants worldwide, generating about 12% 
of civilian electricity use.
5
 In fact, nuclear power already provides 70 percent of carbon-
free electricity in the United States. The energy density of nuclear fuel is another 
desirable quality; the amount of energy in a single uranium fuel pellet is equal to that of 
149 gallons of oil or 1,780 pounds of coal.
6
 
 4 
The relatively recent discovery of the 5f elements coupled with these elements? 
ability to undergo natural fission, manmade fission, and manmade fusion leading to high 
sums of energy sets the foundation for understanding their chemistry.
4,5
  At the first 
publicly accepted report of fission, researchers were primarily interested with harvesting 
the energy released from a fission incident.  Notoriously, the end of World War II was 
brought on by the release of two atomic bombs (Little Boy = 141 pounds of fissile mass, 
Fat Man 56 pounds of fissile mass) on the cities of Hiroshima and Nagasaki in 1945.
8
  
This release of roughly 200 pounds of fissile material, along with other fissile material 
releases in the last 70 years has spurred the fundamental and applied chemistry in attempt 
to be able to understand and ultimately control these atoms in our environment.
8,9
  What 
follows is an overview of the past decade of solid state actinide coordination compounds 
and how these coordination compounds have been related to waste remediation. 
 
 
  
 
 5 
 
  
 6 
5f Coordination Compounds 
 Currently 3936 of the 4165 (94.5%)  structures  containing a 5f element reported 
to the Cambridge Crystallographic Data Centre, CCDC, are composed of structures 
containing Th and U, while 1869 of the 4165 (44.5%) structures contain the UO
2
2+
 ion.
10
 
One reason that the overwhelming majority of the reported actinide structures contain the 
Th or U atoms is because these atoms provide long lived radioisotopes with lower 
radioactive emissions.
9
  The ligands described below have been looked at for liquid-
liquid extraction of trivalent lanthanides and actinides of different oxidation states.  
Generally, multidentate ligands that contains soft donors, such as nitrogen and sulfur, are 
used for such separations. Why?  Because the behavior of the 5f -elements has been 
studied much less, it is a challenging task to predict what ligands would have optimum 
efficiency and selectivity in separations and provide the optimal coordination 
environment for these 5f metal ions in the solid state.
11
 
 
Figure 1 Thermal ellipsoid projection of ammonium type [UO
2
(N,N-bis(2-hydroxy-3,5-
dimethylbenzyl)-4-amino-1-butanol)
2
]. The carbon atoms are depicted as gray, the 
oxygen red, the nitrogen blue, the central uranium atoms green, and the hydrogen atom 
are omitted for clarity.
12
   
 
 7 
 In 2006 and 2007, uranyl complexes coordinated to a series 
aminoalcoholbis(phenolate) ligands were reported.  These ligands provide three hard 
oxygen donors in the form of 2 phenol and one alkyl chain alcohol; the amine group 
provides a hard nitrogen donor. The ultimate goal of these ligands was to be used as 
chelation therapy for overexposure to uranium. These ligands contain an [O,N,O,O?] 
binding pocket and were studied for their chelating effects.  Figure 1 shows the [UO
2
 
(N,N-bis(2-hydroxy-3,5-dimethylbenzyl)-4-amino-1-butanol)
2
] complex. The two 
aminoalcoholbis(phenolate) ligands bind the uranyl metal centers in a bidentate fashion 
with the ligand forming the equatorial plane.  The coordination number of these 
complexes is 6 and is best described as octahedral, with the ?yl oxygens binding at the 
axial positions and the remaining equatorial sites filled by the oxo- donors of the 
aminoalcoholbis(phenolate) ligands, the amine groups are protonated and do not bind the 
uranyl center.
12,13
 
 In the continuation of research, uranyl complexes coordinated with a series of 
diaminobisphenolates were reported.
14,15
  Two types of structures are reported, a 1:1 and 
a 2:1 ligand to metal ratio.  In the 1:1 complexes, the coordination number around the 
uranium center is 7 and is best described as pentagonal bipyramid polyhedron.  The two ?
yl oxygens are found at the axial positions and the equatorial plane is defined by two 
different pentagons depending on whether the central nitrogen in the ligand is an amine 
or an ammonium.  In the amine type ligands, one site is the amine, and four coordination 
sites are filled by oxygens, two from the ligand and two from a bidentate nitrate.  In the 
ammonium type ligands, the nitrogen uranium bond is replaced by a water molecule.  The 
difference between the amine and ammonium type ligand is the protonation of the central 
 8 
nitrogen atom.  In the 2:1 complexes the coordination number around the uranium center 
is 6 and is best described as octahedral.  Figure 2 shows the 2:1 ligand to metal complex 
of [UO
2
(N?,N?-bis(2-hydroxy-3-methoxy-5-(propen-2-yl)benzyl-N-(2-
aminoethyl)morpholine)
2
]
.
2CH
3
CN. The two ?yl oxygens are found at the axial positions 
and the equatorial plane is defined by four oxygens, two from each ligand. 
15
    
 
Figure 2 Thermal ellipsoid projection of the ammonium type [UO
2
(N?,N?-bis(2-hydroxy-
3-methoxy-5-(propen-2-yl)benzyl-N-(2-aminoethyl)morpholine)
2
]
.
2CH
3
CN. The carbon 
atoms are depicted as gray, the oxygen red, the nitrogen blue, the central uranium atoms 
green, and the hydrogen atoms are omitted for clarity.
15
   
 
 
 9 
 In 2007, it was reported that derivatives of the ligand (Figure 3), tributyl 
phosphate (TBP), used in the PUREX process formed coordination structures with uranyl, 
UO
2
2+
, and perrhenate, RhO
4
-
.
16
  The perrhenate ion is of interest because it has been 
shown to be a suitable mimic for pertechnetate (TcO
4
-
), another potentially hazardous 
fission product that is also a  -emitter and readily transportable in aqueous media.
17
   The 
two complexes reported are similar, with the difference being the TBP ligand derivative.  
In both structures, the coordination number of the uranium is seven and best described as 
a pentagonal bipyramid polyhedron.  The ?yl oxygens are found at the two axial positions.  
Three sites of the equatorial pentagon are occupied by oxygens from the perrhenate 
anions.  The remaining two sites are occupied by the oxygens of the TBP derivative 
ligand.
16
    
 
Figure 3 Thermal ellipsoid projection of {UO
2
(?
2
-ReO
4
)(ReO
4
)(TBPO)
2
]
2
. The carbon 
atoms are depicted as gray, the oxygen red, the rhenium metallic blue, the phosphorus 
metallic purple and the central uranium atoms green.
16
   
 10 
 
The first 5f-BTBP, bis-triazinyl bipyridine, complex was reported in 2008.
18
  This 
report also contains three mononuclear and a dinuclear UO
2
-BTBP complex and also a 
dinuclear UO
2
-TPTZ, tripyridyl triazine, complex.  In all five of these structures, the 
coordination number around the uranium site is seven and is best described by a 
pentagonal bipyramid polyhedron with the ?yl oxygens found at the two axial positions. 
In the four BTBP complexes, the BTBP ligand coordinates the uranium center in a 
tetradentate fashion that defines the equatorial plane.
18
    
Schnaars and coworkers, reported three complexes, AnX
2
(
Ar
acnac)
2
 where 
Ar
acnac = (ArNC(Ph)CHC(Ph)O
-
) (Ar = 3,5-tBu
2
C
6
H
3
), containing U and Pu  in 2011.
11
 
Among the interesting features of this report is that both the U and Pu metals in the  +4 
oxidation state were used to prepare complexes and the authors prepared a detailed, 
comprehensive look at that oxidation state.
11
  Two of the isostructural complexes contain 
U(IV) with the difference being the halides, Cl or I,  bonded to the metal center.   The 
Pu(IV) structure will be discusseGEHORZ7KH -ketoiminate ligand, containing a hard 
and soft donor, was used because of its ability to stabilize weak Lewis acids, UO
2
2+
, and 
thus was thought to be able to coordinate to the stronger Lewis acids, An(IV).  The 
coordination number around the uranium center is six and is best described as a distorted 
octahedral polyhedron.  The halides are found at the axial positions and the 
Ar
acnac 
ligands are found in the equatorial plane and are trans to each other, as seen in the 
isostructual PuI
2
(
Ar
acnac)
2
 shown in figure 9.  The differing halides do not affect the 
bonding parameters of the 
Ar
acnac ligand.
11
  
 11 
 
Figure 4 Thermal ellipsoid projection of [UO
2
(3-(2-hydroxybenzylideneamino)propane-
1,2-diol)]
2
?DMF. The carbon atoms are depicted as gray, the hydrogen atoms white, the 
oxygen red, the nitrogen blue, the central uranium atoms green.
19
  
 
 
 Salen-type and Schiff base-UO
2
2+
 structures were reported by our group 
previously.
19-21
  The coordination number of the uranium center, in both the salen-type 
and Schiff base systems, is seven and is best described by a pentagonal bipyramid 
polyhedron, as seen in Figure 4.
19
  The salen-type ligands -called the salen quinoxalinols 
or salqu ligands, were designed with a quinoxaline backbone to enable the readily 
distinguishable properties either by fluorescence or UV-Vis between different metal 
complexes.  In the UO
2
2+
 structures, the ?yl oxygens sit at the axial positions while the 
two oxo- and two aza-coordination sites of the ligand occupy four of the positions in the 
pentagon. The remaining site of the pentagon is occupied by a solvent molecule. In both 
 12 
the Schiff base-UO
2
 (Figure 4) and salen-UO
2 
(Figure 5) compounds the ligand must 
twist from a planar conformation to accommodate the uranyl ion. This results in a large 
change in the overlap of the ? -bonds in the conjugated back bone, and consequently, a 
large change in the spectroscopy.
20
  
 
Figure 5 Thermal ellipsoid projection of UO
2
(2-quinaxilinol). The carbon atoms are 
depicted as gray, the hydrogen atoms white, the oxygen red, the nitrogen blue, the central 
uranium atom green.
20
 
  In the asymmetric Schiff-base structures, the ?yl oxygens sit at the axial positions 
while the equatorial pentagonal coordination is very different. Two ligands bind two 
metals and exclude the solvent molecule, forming a dinuclear U
2
O
2
 species.  This U
2
O
2
 
 13 
species is composed of two uranium sites, bridged by an alkoxyl and hydroxyl oxygen.  
This U
2
O
2
 core is reported as stable to hydrolysis and transamination and could 
potentially be used to remediate waste stored under alkaline conditions. The shape of this 
species forms a diamond with each vertex alternating between uranium atom and oxygen 
atom. (See example with ligand (E)-3-((2-hydroxybenzylidene)amino)propane-1,2-diol - 
Figure 4)  The coordinating pentagon around the metal ion is composed of a phenolic 
oxygen, imine nitrogen, bridging alkoxyl and hydroxyl group with the remaining site of 
the pentagon occupied by a solvent molecule.
19
 These ligand systems offer the U
?
U 
interaction found at 3.8794 ? in Figure 4 of [UO
2
(3-(2-
hydroxybenzylideneamino)propane-1,2-diol)]
2
?C
3
H
7
NO. In the series of these complexes, 
prepared with different substituents on the aryl backbone, the resultant complexes were 
always dinuclear 2:2 metal:ligand complexes. Simple extraction studies proved that they 
could be effective for removing uranyl from aqueous solutions (up to 99% in 24 hours); 
however, the presence of iron or copper in mixed solutions would later demonstrate 
complications to selective extractions.  Hydrolysis of this extraction agent does occur, but 
at extreme pH, conditions (i.e.  1-3 and 13-14); this is important as nuclear waste is found 
at high and low pH and a one ligand processing system will need a stable ligand over a 
wide pH range.
19,22,23
  
 With additional bridged structures, an attempt was made to limit the formation of 
dinuclear complexes to prepare a 1:1 ligand to metal complex with the preparation of a 
2,2'-((1E,1'E)-((2-hydroxypropane-1,3-
diyl)bis(azanylylidene))bis(methanylylidene))diphenol ligand.
23
  In resulting 
complexation structures, the coordination number of the uranium site is seven and is best 
 14 
described as a pentagonal bipyramid polyhedron.   The ?yl oxygens sit at the axial 
positions while the equatorial pentagonal coordination is different.  The 1:2 ligand to 
metal pentagon is composed of a phenolic oxygen, imine nitrogen, bridging alkoxyl and 
hydroxyl group with the remaining site of the pentagon occupied by a solvent molecule.  
The 2:2 ligand to metal pentagonal geometry is the same as the 2:1, in that the 
coordination bite angles and bond distances are very similar, but one bridging hydroxyl 
group has been replaced by a coordinating solvent molecule the bridging hydroxyl group 
in the 2:1 system.  Coordinated to uranyl, these Schiff base complexes are very stable - in 
particular as compared to their transition metal counterparts, and may be useful in the 
alkaline nuclear waste solutions.
19,22,23
 This still may be of use as a final back extraction 
polishing step in that the ligand could be used to retain uranium in organic solutions after 
adjusting to a basic pH which would release complexed transition metals.
24,25
 
 15 
 
Figure 6 Thermal ellipsoid projection of [cyclo[6]pyrrole (UO
2
)].  The carbon atoms are 
depicted as gray, the hydrogen white, the oxygen red, the nitrogen blue, the central 
uranium atoms green.
26
 
 
 
 The all aza [cyclo[6]pyrrole(UO
2
)] coordination complex was reported in 2007.
26
  
The ligand was first noted in the synthesis of cyclo[8]pyrrole.
27
 The authors held that the 
cyclo[6]pyrrole would bind uranyl more readily than the earlier reported cyclo[8]pyrrole 
because of its cavity size and favorable donor number. The coordination number of the 
uranium site is 8 and is best described as a hexagonal bipyramid, as seen in Figure 6.  The 
?yl oxygens are found at the axial position, and the nitrogen atoms from the ligand define 
 16 
the hexagonal equatorial plane.  This is the first metal complex of the cyclo[N]pyrrole 
series of expanded porphyrins.
26
 
  In 2009 and 2010, uranyl structures of the bis(Me-3,2-HOPO), 3-hydroxy-N-
methylpyridin-2-one, ligand derivatives were reported.
28,29
 The uranium sites in the 
reported structures have a coordination number of seven and are best described as  
bicapped pentagonal polyhedra.   This ligand architecture coordinates the uranyl unit in a 
tetradentate fashion, through the four hydroxypyridonate oxygens, leaving one site open 
for coordination through another ligand or a solvent.  In 2011, two uranyl structures of a 
MeTAM - methyl terephlalamide - ligand were reported.
30
 Previous studies have 
demonstrated that the MeTAM ligand can act as a decorporation agent, and it was found 
to be more efficient in reducing the [UO
2
2+
] in the kidneys and deposited bone than the 
hydroxypyridonate ligands.
31,32
  
 17 
 
Figure 7 The ball and stick projection of [NpO
2
([18]crown-6)]
+
.  The perchlorate anion 
and the hydrogen atoms have been omitted for clarity.   The carbon atoms are depicted as 
gray, the oxygen red, the central neptunium atom green. 
33
  
 
  Coordination structures that contain neptunium have been few and far between. 
The first transuranic ether inclusion complex, [NpO
2
([18]crown-6)][X]  (where X = ClO
4
-
 
or CF
3
SO
3
-
), with single crystal diffraction data, was reported by Clark and coworkers in 
1998 (See Figure 7). The NpO
2
+
 ion is of particular interest because of the problems 
associated with extracting it from high level nuclear waste, stemming from the low 
positive charge and relatively high solubility in aqueous media of the neptunyl ion.
33
  
This also makes neptunyl of great potential environmental and health consequence, 
 18 
because it could be easily transported in ground water or introduced into the food chain 
after a waste spill.
34,35
  The Np=O bond length of 1.800 (5) ? is unusually short for an 
NpO
2
+
 ion; it is found at a distance that is 0.05 ? shorter in the [NpO
2
(H
2
O)
5
]
+
 ion.
33
 The 
[18]crown-6 ligand completely encapsulates the NpO
2
+
 ion.  The Np(V) center is best 
described by an approximate hexagonal bipyramid.  The short ?yl oxygens are found at 
the axial positions and the ligands O
ether
 coordinate forming the equatorial hexagonal 
plane.  
 A neptunium
v
-hexaphyrin expanded porphyrin type complex was reported in 
2001.
36
  The neptunium(V) center has a coordination number of 8 and is best described as 
a hexagonal bipyramidal polyhedron.  The ?yl oxygens are found at the axial positions, 
with the remaining six coordination sites filled by nitrogen donors from the ligand.  The 
hexaphyrin ligand does have a slight twist when bound to the NpO
2
+
 center, but the 
distortion is not as pronounced as in the uranyl hexaphyrin structure described in the 
same paper.  The authors reason that the larger ionic radius of the NpO
2
+
 is a better fit for 
the hexaphyrin ligand as opposed to the uranyl unit.
36
 It was later characterized with 
substituted versions of this ring to determine how this distortion affects coordination.
37
 
This was the first reported all aza- coordinating system for neptunium, and its selectivity 
for actinides and intense color were characterized in potential sensing applications.
38-41
 
 Of the actinide structures reported in the CCDC, the 134 neptunium and 77 
plutonium-containing crystal structures represent 3.2 and only 1.8% of the actinide 
compounds reported respectively (CCDC database search). The remaining 0.5% of the 
actinides structures reported are the rest of the actinides besides those previously 
described (i.e. not U, Th, Pu, or Np). This is a problem as the fundamental bonding 
 19 
parameters and coordination chemistry behavior need to be better understood to be able 
to intelligently design ligands for separations, perform detailed calculations, and 
ultimately to formulate new processes using these ligands.     
 
Figure 8 Projection of [Pu(5LIO(Me-3,2-HOPO))
2
], one ligand shown as a ball and stick 
and the other as tube, lacking non hydrogen bonding hydrogens for clarity. The carbon 
atoms are depicted as gray, the oxygen red, the nitrogen blue, and the central plutonium 
atom green. 
42
 
 
 
In 2000 the first structure reported of an organic extraction agent with a 
plutonium metal resolved by single crystal analysis was [Pu(1)
2
(NO
3
)
2
][(NO
3
)
2
], where 1 
is the trifunctional ligand 2,6-[(C
6
H
5
)
2
P(O)CH
2
]
2
C
5
H
3
NO and can also be abbreviated to 
NOPOPO.
42
  The coordination number around the plutonium center is 10 and is best 
 20 
described as a distorted bicapped square antiprism.  All ten of the inner sphere 
coordinating atoms are oxygens.  Two of the ligands bind the plutonium center in a 
tridentate fashion, each ligand binds once through the O
pyridine N-Oxide
 
and twice through the 
O
phosphoryl
 sites.  The M-O
ligand
 bond distances of the Pu(IV) structure are shorter than the 
Th(IV) complex.    While the actinide contraction is not as linear as the lanthanide 
contraction, it still exists and these systems are evidence of this.
43
  Typically, a ligand that 
forms complexes with the lighter actinides forms shorter bonds with the heavier 
actinides.
42
  Later, the compound [Pu(2)
2
(NO
3
)
3
+
][Pu(NO
3
)
6
 
2-
]
0.5
 was reported, where 
2 is the bifunctional 2-[(C
6
H
5
)
2
P(O)CH
2
]C
5
H
4
NO.
44
  The coordination number of this 
complex is 10 and is best described as an average of a bicapped antiprism and a 
sphenocorona.  There are two idealized 10 vertex polyhedra; one is a bicapped antiprism, 
and the other is a sphenocorona. The complex is not described by either of these 
polyhedra, rather it is better described as a combination of the two. These complexes are 
examples of and could lead to the further development of phosphinopyridine ligands in 
separations of nuclear waste.
44
  
  Linear and cyclic hydroxamates containing the building block 1-amino-5-
hydroxamino-pentane as a building block have been found in the naturally occurring 
compounds known as siderophores, that bacteria have as a way to sequester naturally 
occurring iron.
45
  These complexes were of interest because they are potentially useful in 
medical treatments as chelators for iron and aluminum overload.
31,45-49
 The first 
plutonium-siderophore complex to be structurally characterized was 
[Al(H
2
O)
6
][Pu(DFE)(H
2
O)
3
]
2
(CF
3
SO
3
)
5
.
14H
2
O, where DFE is an abbreviation for 
desferrioxamine E. The coordination number around the plutonium metal center is 9, and 
 21 
can be best described as a distorted tricapped trigonal prism.  The ligand coordinates the 
metal center through six oxygens, three from O
carbonyl
 and three from the O
oximate
.  Three 
water molecules complete the coordination sphere. This compound is the first discrete 
molecule structurally characterized with a plutonium(IV) ion that is 9 coordinate.
50
 These 
siderophore type complexes are interesting, as they biologically function to separate a 
metal from the environment, transport it across an organic layer, and release the metal 
under the desired conditions.
50
  The DFE ligand undergoes the same conformational 
changes when binding Pu
IV
 as Fe
III
 ions. This fact coupled with the known recruitment of 
iron from the environment into a cell is via DFE leads to the hypothesis that the Pu(DFE) 
complex could cross the cell membrane with relative ease as compared to the relatively 
aqueous insoluble Pu
IV
(OH)
4
 and Pu
IV
O
2 
species.   
 The first structure of a plutonium
IV
 hydroxypyridonate (HOPO) was reported in 
2005. The complex is modeled after coordination systems found in siderophores with two 
N-methyl-3-hydroxy-2-pyridinone groups linked by a 5-membered ether linker. The 
coordination number of the plutonium atom is 8 and best described as a bicapped trigonal 
prism.  The metal complex is formed by two of the 5LIO(Me-3,2-HOPO) ligands with 
one plutonium atom.  The 5LIO(Me-3,2-HOPO) ligand contains two types of oxygens, 
the phenolic and amide nitrogen oxygens.  Four oxygens from each ligand bind the 
plutonium metal in a sandwich type complex, as seen in figure 8. In part because of the 
flexible geometry allowed by the Pu ion, this is the first structure to have two different 
chiralities of metal complex in one unit cell.
51
 This structure was later followed by other 
related 1,2-HOPO Pu(IV) and Pu(IV)-maltol structures, which were reported with the 
comparable Ce(IV) structures for comparison. There was a remarkable difference 
 22 
between these structures which had very dissimilar geometries although they had similar 
size metal ions, and it points to a significant concern about the viability of Ce(IV) as a 
model for Pu(IV).
52,53
 
 
  
 
Figure 9  Projection of PuI
2
(
Ar
acnac)
2
, model shown as a ball and stick projection, lacking 
hydrogens for clarity. The carbon atoms are depicted in gray, the oxygen atoms red, the 
nitrogen atoms blue, the iodine atoms as purple and the central plutonium atom is in 
green.
11
 
 
 As described above, three isostructural compounds with the general formula 
AnX
2
(
Ar
acnac)
2
 were reported. The PuI
2
(
Ar
acnac)
2
 comples is shown in figure 9. The 
starting material for the Pu isostructure was Pu
0
, partially because of the lack of suitable 
Pu(IV) starting materials.
11
  This structure reported is the first example of a Pu-I bond. 
The actinide contraction and ionic bonding models alone are not enough to explain the 
 23 
difference in the An-O and An-N bond lengths of the PuI
2
(
Ar
acnac)
2
 and the UI
2
(
Ar
acnac)
2
 
isostructures. The 
Ar
acnac ligand may be a useful probe in elucidating an all enclusive 
comparative bonding study of the actinides because it is not limited by cavity size or 
sterics.  The solid state plutonium structures reported within have one common feature, 
excluding PuI
2
(
Ar
acnac)
2
; this feature is that the metal center is completely bound by 
oxygen atoms. 
11
 
 In general soft donors are preferred for separations purposes, yet, with the 
majority of reported structures, hard donors appear favored for the isolation of single 
crystals suitable for X-ray diffraction. One reason for the lack of plutonium containing 
coordination structures reported is the lack of readily available starting materials.  This is 
complicated by the fact that materials must be carefully handled and that plutonium can 
have up to five oxidation states in aqueous solutions. Thus, preparing solutions 
containing ions in a single oxidation state for use in metal complexes requires additional 
preparation.
9
  Because of these facts regarding the complications of working with 
plutonium no reactions containing plutonium were completed in my research career.  
The majority of this text is devoted to structural elucidation of thorium and 
uranium containing coordination compounds and how these structural characterizations 
are related to the observed optical properties. The hope is that this research has broadened 
the scope of the solid state actinide containing coordination compounds and that these 
new insights may lead to long term, solid state, waste remediation solutions. 
  
 
 
 24 
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 27 
Chapter 2: Solid state structural elucidation of the Th
IV
, UO
2
VI
, 
and U
IV
 cyanometallates  
 
5f-Cyanometallate Coordination Complexes 
 
 Increasing the use of nuclear energy is one alternative to generate significant 
amounts of energy with low atmospheric emissions;
1
 however, the extraction and use of 
uranium for nuclear fuel leads to many environmental concerns including long term 
storage and remediation.
2-6  
In the United States nuclear power plants  each 100 million 
watts of electric capacity (mWe) produced required  0.18 metric tons of uranium metal.
10
  
Thorium is also being used increasingly in the design of new reactor systems, and 
thorium is estimated to be four times more abundant than uranium.
11
 One strategy in the 
development of improved methods of uranium processing is to continue to further our 
understanding of actinide chemistry with detailed characterization of actinide 
coordination complexes.
11
 For these reasons, the fundamental chemistry of actinide 
complexes has become of broad interest.
9,12-18
 
Metal complex salts containing tetracyanoplatinate (TCPt) anions have been 
investigated for roughly 200 years.
19
 Initial interest was in the differing colors of the 
complexes. The optical properties of these complexes could be altered by simply 
changing the cation in the solid state; the clear, colorless aqueous solutions were not as 
optically elegant.
19
 These compounds have been reported in some alluring applications: 
they have been suggested for use in polymer electrolyte membrane fuel cells,
20
 as catalyst 
precursors,
21 
and in vapochromic sensing.
22
 Prussian blue and Berlin blue analogs contain 
 28 
identical cyanide linkages between metal centers as the TCPt complexes.   These cyano-
bridged metal, M-N-C-M?, compounds have been shown to demonstrate intriguing 
magnetic behavior.
23-26
 
In the mid-1980s, Gliemann and Yersin reviewed the properties of 36 solid state 
TCPt compounds known at that time? ranging from lithium as the lightest to thulium as 
the heaviest cation in the Li
2
[Pt(CN)
4
]?4H
2
O and Tm
2
[Pt(CN)
4
]
3
?21H
2
O compounds 
respectively.
19
 This review outlined several structural features and parameters inherent to 
the TCPt class of compounds all relating to the quasi one-dimensional Pt chains observed 
in the solid-state structures.  Quasi one-dimensional chains are formed in the solid state;  
platinophilic interactions may guide the square planar TCPt anions tendency to stack.  
These parallel columns are thus thought to be responsible for the optical properties of this 
class of compounds.
19
 The distance, R, between adjacent Pt atoms in these chains is 
considered critical in determining the characteristic emission properties. A simple 
equation has been derived to relate observed emission to the distance, R, between Pt 
atoms.
27  
It has been noted that this distance can be altered by pressure, temperature, 
choice of cation, or magnetic fields.
19
 
These early solid state TCPt compounds were noteworthy because of their 
striking optical features in the visible range.
19
 Since this review was written, more than 
30 years ago, the TCPt class of compounds has been expanded.
27-30
 The pseudo one-
dimensional Pt
?
Pt structural feature was allowed in the initial work, because the solvent 
used for these compounds, primarily, was H
2
O.  Since the early work in aqueous 
chemistry, several other polar solvents have successfully been used such as dimethyl 
sulfoxide, N,N-dimethyl acetamide,  and N,N-dimethyl formamide;
28
 however,  solvation 
 29 
of the cation with larger solvent molecules tends to preclude the formation of the pseudo 
one-dimensional Pt
?
Pt interactions and subsequent visible emission.  Further extension 
of this class continued with the addition of aromatic ligands coordinating to the cationic 
metal center allowing for subsequent tuning of R in the TCPt chains. This also aided in 
the characterization of internal energy processes with the sensitization of weakly emitting 
lanthanide cations.
29
  Work in this field after the Gliemann and Yersin review has 
focused on solvent and ancillary ligand effects and not incorporated actinide metal ions.
9
 
Recent research on TCPt systems has involved the incorporation of lanthanides into 
novel TCPt systems.
27,29,31-33
 The complexation of the lanthanides with transition metal 
cyanides have resulted in new compounds with a CN
?
 bridging the d and 4f metal centers.  
As expected, the optical properties of these compounds are of interest as the LnTCPt 
systems have been shown to undergo intramolecular energy transfer processes that can 
either enhance
29,34
 or weaken
32
 the lanthanide emission.
30,35
 The discovery of transition 
metal cyanide complexes with interesting magnetic behavior coupled with a report 
demonstrating strong ferromagnetic coupling between an actinide ion and transition 
metals has sparked our interest in exploring the magnetic properties of the f orbitals by 
bridging the 5d and 5f metals with a CN
? 
ligand.
31,33
  These reports support the idea of 
enhanced magnetic properties with the possibility of forming discrete molecules 
exhibiting slow magnetic relaxation, known as single-molecule magnets (SMMs).
33
  At 
present, the magnetic properties of cyanoplatinate-based lanthanide systems have not 
been described.  As compared to the 5f orbitals of the actinides, the radial extension of 
the 4f orbitals of the lanthanides are smaller and therefore these latter orbitals are more 
ionic in nature. The essential lack of covalency by the 4f orbitals is thought to not allow 
 30 
strong enough orbital overlap to provide magnetic coupling in the 4f?5d CN bridged 
compounds.  
Cyanide metallocenes
31
 and cyanide bridged bimetallic 3d-5f complexes
36
 have been 
reported recently, with evidence to support increased covalent character in the An-C 
cyanide bond of the metallocenes. Our interest lies in the actinides and their 5f orbitals, 
rather than the 4f orbitals, because the radial extension of these orbitals may provide 
enough overlap to significantly raise the relaxation barrier height and thus increase the 
possibility of cyano bridged 5d-5f SMMs. Compounds containing the tetracyanoplatinate 
anion have been characterized by their one dimensional Pt-Pt chains,
37
 and a simple 
equation has been derived to determine the Pt-Pt spacing using UV-visible bands.
27
   The 
TCPt anion also offers the ability of the terminal nitrogens to bind metals in low and high 
oxidation states, with multiple binding modes.
29-31,34,35
 
Here, we report on the first 5f-element TCPt compounds, 
Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O (Th1), Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O 
Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O  (Th2),  K
3
[(UO
2
)
2
(OH)(Pt(CN)
4
)
2
]
2
?NO
3
?1.5H
2
O  
(U3), {U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O  (U4), {Th
2
(H
2
O)
10
(OH)
2
[Pd(CN)
4
]
3
}?8H
2
O  
(Th5), {(UO
2
)
2
(C
2
H
6
SO)
4
(OH)
2
[Ni(CN)
4
]}  (U6), [Th(C
2
H
6
SO)
9
][Pt(CN)
4
]
2
?4H
2
O (Th7), 
and [Th(C
2
H
6
SO)
8
][Fe(CN)
6
]?NO
3
 (Th8)   of the actinide tetracyanometallate, 
An
x
[M(CN)
4
]
y
, class of compounds. They have been characterized by confocal Raman 
spectroscopy and single crystal X-ray diffraction.  It was remarkable that the thorium 
compounds, Th1 and Th2, emitted while the uranyl compound, U3, lacked any observed 
emission.
9
   These compounds contain unique structures illustrating dimeric actinide 
species. The absence of any significant charge transfer emission in the visible range as 
 31 
compared to the platinum starting material for {U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O is 
unusual because of the presence of pseudo one-dimensional Pt
?
Pt chains in this 
compound.  Confocal Raman spectroscopy of the cyanide stretching region provides 
insight into the binding domain (mono- bi- tri- tetradentate) of the tetracyanometallates in 
these novel structures.   The synthesis for compounds Th1, Th2, U3, U4, Th5, U6, Th7, 
and Th8 can be found below. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 32 
Synthesis of Actinide Cyanometallates 
Caution! The Th(NO
3
)
4
?6H
2
O UO
2
(NO
3
)
2
?6H
2
O and UCl
4
 used in this study contained 
depleted uranium, standard precautions for handling radioactive materials or heavy 
metals, such as uranyl nitrate and thorium nitrate, were followed. 
 
 
Potassium tetracyanonickelate (II) hydrate (99.9%, Strem), potassium 
tetracyanopalladate(II) hydrate (98%, Strem), and potassium tetracyanoplatinate(II) 
hydrate (98%, Strem),  UO
2
(NO
3
)
2
?6H
2
O (98%, J. T. Baker), Th(NO
3
)
4
?6H
2
O (99%, 
Fluka), and  DMSO (99.9%, ACROS), ortho-phenylendediamine (98%, Acros), 2,3-
diaminophenazine (90%, Aldrich) were used as received without further purification.  
Deionized H
2
20
FPZDVREWDLQHGDQGXVHGRQVLWH8&O
4
 was synthesized by 
the reaction of U
3
O
8
 with hexachloropropene reported by Hashimoto, et al.
1
  
 
 
General Synthesis:  Complexes Th1 and Th2 were synthesized by weighing out a 
roughly equimolar amount of Th(NO
3
)
4
.
6H
2
O and K
2
[Pt(CN)
4
]
.
3H
2
O and dissolving in 
H
2
O.  The addition of dilute HNO
3
 was used to synthesize complex 1.  Complex 3 was 
synthesized in the same fashion, an equimolar amount of UO
2
(NO
3
)
2
.
6H
2
O and 
K
2
[Pt(CN)
4
]
.
3H
2
O were dissolved in H
2
O.  Crystals suitable for X-ray diffraction were 
observed within 2-4 weeks, and yields were found to be 85, 80 and 56% for Th1, Th2, 
and U3 respectively. 
 30 
Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O (Th1) was prepared by dissolving 0.0250 g (0.04 mmol) of 
Th(NO
3
)
4
.
6H
2
O and 0.0235  g (0.06 mmol) of K
2
[Pt(CN)
4
]
.
xH
2
O in 3 mL of H
2
O in a test 
tube.  The pH was brought to 2.5 with a small amount of 0.01 M KOH.  The test tube was 
placed in a slow evaporation chamber, after 29 days green-yellow plates suitable for 
single crystal X-ray    diffraction were observed. 
 
Th
2
(H
2
O)
10
(OH)[Pt(CN)
4
]?5H
2
O (Th2)  was prepared out by dissolving 0.0246 g (0.04 
mmol) of Th(NO
3
)
4
.
6H
2
O and 0.0237  g ( 0.06 mmol) of K
2
[Pt(CN)
4
]
.
3H
2
O in 3 mL of 
H
2
O in a test tube.  The test tube was placed in a slow evaporation chamber, after 14 days 
green-yellow plates suitable for single crystal X-ray diffraction were observed.   
 
K
3
[(UO
2
)
2
(OH)(Pt(CN)
4
)
2
]
2
?NO
3
?1.5H
2
O (U3) was prepared dissolving 0.0248 g  (0.05 
mmol) of UO
2
(NO
3
)
2
.
6H
2
O and 0.0190 g (.05 mmol)of K
2
[Pt(CN)
4
]
.
xH
2
O in 3 mL of 
H
2
O.  The test tube was placed in a slow evaporation chamber, after 20 days yellow 
plates suitable for single crystal X-ray diffraction were observed. 
 
{U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O Complex U4 was synthesized in an inert atmosphere, 
employing  Schlenk techniques to avoid the inclusion of O
2
 into the system.  Nitrogen gas 
was bubbled through H
2
O contained in a Schlenk flask to exchange the dissolved O
2 
gas 
with N
2 
gas.  The H
2
O was cycled three times using a freeze-pump-thaw method to 
completely degas the H
2
O. A portion of 0.0216 g (0.0569 mmol) of UCl
4
 was weighed 
out inside an argon atmosphere glove box and placed into a 200 mL Schlenk flask.  
Slightly less than 1 equivalent, 0.0207 g (0.0549 mmol) of K
2
[Pt(CN)
4
]?3H
2
O, was 
 31 
weighed out and placed into a 50 mL Schlenk flask.  With all three Schlenk flasks 
connected to the Schlenk line, a cannula was used to transfer the deoxygenated H
2
O to 
the Schlenk flasks containing the starting materials. The solutions were stirred to allow 
the solids to dissolve. The K
2
[Pt(CN)
4
]?3H
2
O solution was then transferred by cannula 
into the Schlenk flask containing the UCl
4 
solution.  A small amount of precipitate that 
formed was removed by filtration. The mother liquor was placed in a ?19 qC freezer 
where crystals suitable for single crystal X-ray diffraction (XRD) were observed to have 
formed after 6 days. Crystalline yield was not determined as the air sensitivity of the 
sample is significant and therefore, cannot be accurately weighed on the bench. The 
presence of H
2
O precluded sample manipulation or weighing in the Ar inert atmosphere 
glove box.  
 
{Th
2
(H
2
O)
10
(OH)
2
[Pd(CN)
4
]
3
}?8H
2
O  Complex Th5 was synthesized by weighing out 
0.0200 g (0.0387 mmol) of Th(NO
3
)
4
?6H
2
O and 0.0146 (0.0506 mmol) of 
K
2
[Pd(CN)
4
]?xH
2
O. Each was dissolved in a minimal amount of H
2
O. The 
K
2
[Pd(CN)
4
?xH
2
O solution was layered onto the Th(NO
3
)
4
 solution in a 5 mL test tube.  
The test tube was exposed to atmospheric conditions in a slow evaporation chamber 
where crystals suitable for single crystal XRD were observed to have formed after 27 
days. Crystalline yield of 0.0148 g (67%). 
 
{(UO
2
)
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]}  Complex U6 was synthesized by weighing out 
0.0251 g (0.0500 mmol) of UO
2
(NO
3
)
2
?6H
2
O and 0.0140 g (0.0581 mmol) of 
K
2
[Ni(CN)
4
]?xH
2
O.  Each was dissolved in a minimal amount of H
2
O.  The 
 32 
K
2
[Ni(CN)
4
?xH
2
O solution was layered onto the UO
2
(NO
3
)
2
?H
2
O solution in a 5 mL test 
tube.  The test tube was exposed to atmospheric conditions where crystals suitable for 
single crystal XRD were observed to have formed after 32 days. Crystalline yield of 
0.0118 g (45%). 
 
 
[Th(C
2
H
6
SO)
9
][Pt(CN)
4
]
2
?4H
2
O Complex Th7 was synthesized by weighing out 
0.0200 grams (0.0387 mmol) of Th(NO
3
)
4
.
6H
2
O and 0.0146 grams (0.0387 mmol) of 
K
2
[Pt(CN)
4
]
.
3H
2
O. Each was dissolved in the smallest amount of DMSO neccessary to 
produce a clear solution. Solutions were heated to aid the dissolution. The 
K
2
[Pt(CN)
4
]
.
3H
2
O solution was transferred to the Th(NO
3
)
4
.
6H
2
O solution via pipette. 
The solution was allowed to mix and it remained clear and colorless immediately after 
transfer.  The solution was allowed to cool at room temperature and left open to air. 
Suitable crystals for single crystal XRD were observed after 10 days. 
 
[Th(C
2
H
6
SO)
8
][Fe(CN)
6
]?NO
3
 Complex Th8 was synthesized by weighing out 
0.0200 grams (0.0387 mmol) of Th(NO
3
)
4
.
6H
2
O and 0.0143 grams (0.0387 mmol) of 
K
3
[Fe(CN)
6
]
.
3H
2
O. Each was dissolved in a minimal amount of DMSO. In addition to 
heating, the K
4
[Fe(CN)
6
]
.
3H
2
O solution was filtered twice through glass wool before 
added to the Th(NO
3
)
4
.
6H
2
O solution via pipette. The solution was allowed to mix and 
remained clear and colorless immediately after transfer. The solution was allowed to cool 
at room temperature and left open to air. Suitable crystals for single crystal XRD were 
collected after 12 days. 
 33 
5f-Cyanometallate Coordination Complexes 
Th(H
2
O)
7
[Pt(CN)
4
]
2
.
10H
2
O (Th1) 
 
 
 The structure of Th1 (Figure 10) is molecular and consists of 
[Th(H
2
O)
7
(Pt(CN)
4
)
2
] monomers.  The Th metal center is coordinated by two nitrogens 
from the tetracyanoplatinate anions and seven oxygens from water molecules. The overall 
coordination environment of the Th site is nine, which is best described as a tricapped 
trigonal prism. The Th-O bonds range from 2.420(4) to 2.494(4) and the two Th-N bonds 
are significantly longer at 2.552(5) and 2.571(4) ?.  The Th-O bonds correlate well with 
reported Th-OH
2
 data.
38 
The Th-N bonds are longer than reported Th-N bonds; 
39,40
   
however these complexes are the first reported N bonded cyanide complexes coordinated 
Figure 10  Asymmetric unit of Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O (Th1).  Atoms as shown are 
labeled:  Th in green, O in red, N in blue, C in grey, and Pt in metallic blue.
9
 
 34 
to  thorium The packing diagram of Th1 (Figure 11) shows the extension of quasi one 
dimensional linear chains with non-equidistant Pt-Pt distances at 3.371 and 3.351 ?.  
These distances are ~0.1 ? longer and consistent with the shorter wavelength emission 
(~50 nm shorter) relative to that compound. These interactions are formed by the 
interaction of monomers between two tetracyanoplatinate anions. 
 
 
 
 
  
 
 
 
Figure 11  Packing diagram of Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O (Th1).  Atoms as shown 
are labeled:  Th in green, O in red, N in blue, C in grey, and Pt in metallic blue.
9
 
 35 
Th
2
(H
2
O)
10
(OH)[Pt(CN)
4
]?5H
2
O (Th2)   
 
The structure of Th2 (Figure 12) consists of one-dimensional 
[Th
2
(H
2
O)
10
(OH)
2
(Pt(CN)
4
)
3
]
 
chains.  Th dimers are formed by linking each Th site with 
hydroxyls at the bridging oxygen position as seen in figure 12.  The Th metal centers are 
each coordinated by five water molecules.  The overall coordination environment of the 
Th site is nine, and the coordination geometry about the metal center is best described as 
a tricapped trigonal prism.  The Th-O and Th-1ERQGVUDQJHIURP?DQG
? ? repectively.  The Th-O bonds correlate with the Th-OH
2
 data, with 
Figure 12   Projection of Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O (Th2) showing the extension 
of the 1 dimensional chain and the Th-O-Th units.  Atoms as shown are labeled:  Th in 
green, O in red, N in blue, C in black, and Pt in magenta.
9
 
 36 
the Th-OH being slightly truncated at 2.348(4) ?.
38
  The Th-N bonds are longer than 
 
Figure 13   Packing diagram of Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O (Th2).  Atoms as 
shown are labeled:  Th in green, O in red, N in blue, C in grey, and Pt in magenta.
9
 
 
 reported bonds and probably better described as a dative interaction.
39,41
  The elongation 
of the one dimensional structure is visualized in Figure 12 through the Th-O-Th-TCPt-
Th-O-Th-TCPt-Th-O-Th chain. The packing diagram of 2 (Figure 13) shows the 
extension of quasi one dimensional chains with equal Pt-Pt distances at 3.272 ? 
representing an equidistant linear chain. These interactions are formed by the interaction 
of dimers between two tetracyanoplatinate anions. 
 
 37 
K
3
[(UO
2
)
2
(OH)(Pt(CN)
4
)
2
]
2
?NO
3
?1.5H
2
O  (U3) 
The structure of U3 (Figure 14) consists of a complex three dimensional lattice made 
from units of [UO
2
(OH)(Pt(CN)
4
)
4
].  The lattice in 3 consists of layers of cubes with 
Figure 14 Packing diagram of K
3
[(UO
2
)
2
(OH)(Pt(CN)
4
)
2
]
2
?NO
3
?1.5H
2
O (U3) viewed 
along the c axis. K
+
, (NO
3
)
-
, waters of hydration and hydrogen atoms omitted for clarity. 
Atoms as shown are labeled:  U in yellow, O in red, N in blue, C in black, and Pt in 
purple.
9
 
 
 38 
TCPt anions at the eight vertices.  In turn, these layers are bridged by hydroxyl units 
between uranyl units.  The uranium sites are cis bridged within each respective cube and 
are found at the midpoint of each edge of the cube. The overall coordination environment 
of the U site is seven, which is best described as a pentagonal bipyramid. Three oxygens 
coordinate the U center. The ?-\O?R[\JHQGLVWDQFHV8?2DQG8?2DUHVLJQLILFDQWO\
shorter  at 1.774(12) and 1.720(12) ?, forming  a O?U?O angle of 179.1(5)?; this 
confirms the retention of the uranyl subunit. The third oxygen, a hydroxyl group, 
coordinates the uranium at a distance of 2.310(6) ?.  The four U-N bonds range from 
2.482(12) to 2.531(14) ?. The packing of U3 in the structure does not result in quasi one 
dimensional chains as seen in Th1 and Th2. Instead, in the structure of U3, dimeric Pt?Pt 
interactions are observed at 3.2214(15) ?.   
These interactions are found between the layers of cube vertices giving the spacing 
between layers. The Pt?Pt distances are shorter in complex U3 as compared to complexes 
Th1 and Th2, and the expected emission should be blue shifted relative to these; 
however, the lack of emission from U3, as observed in the emission spectra (Chapter 3), 
may be caused by the missing quasi one dimensional Pt-Pt chains. 
 While the nature of the energy sink is not definitely known at this time, we 
believe that the source is most likely due to its open-framework nature. Within the 
channels of the structure there is a large amount of thermal motion of the potassium and 
nitrate ions as well as the hydrate water molecules.  This is seen in the large thermal 
parameters found in the anisotropic refinement of these nitrate ions and water molecules.  
These large thermal parameters could be explained in at least two different ways.  First, it 
would be  probable that within this metal framework of U3 that the charge balance nitrate 
 39 
ions and waters of hydration are weakly structurally ordered. This weak ordering allows 
the atom positions of the nitrate and water molecules to ?drift? from one unit cell 
compared to another.  This positional disorder would lead to elongated thermal 
parameters.  Second, it is plausible that an energy transfer mechanism exists in the 
compound that results in the lack of visible emission of both the uranyl and TCPt 
portions, but rather results in non-radiative vibrational relaxation of the channel 
components. Further studies, such as low-temperature emission, are needed to support 
this hypothesis. 
 
 40 
 
 
{U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O  (U4)    The structure of U4 has two dimensional, 
bonding interactions, contains U(IV) as the actinide metal cation, and consists of 
[U(H
2
O)
5
(O)(Pt(CN)
4
)] units.  Three tetracyanoplatinate anions and five water molecules 
coordinate the U(IV) metal center.  One additional oxygen bridges two uranium sites to 
complete the coordination sphere as shown in Figure 15.  The U(1)-O(1) bond distance at 
Figure 15 Projection of {U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O with lattice vectors shown. 
Hydration water molecules and hydrogens have been removed for clarity.
7
  
 
 41 
2.0706(7) ? and the U-O-U bond angle of 180? corresponds well with another U-O
oxo
-U 
bridged species.
17
  The overall coordination environment of the U(IV) site is nine, and 
this is best described geometrically as a tricapped trigonal prism.  There are two distinct 
crystallographic tetracyanoplatinate anions in this structure. The structure is extended in 
two dimensions by the tetracyanoplatinate anions containing Pt1, which are tridentate and 
bridge three U sites, and the oxo bridge which links together two U sites as shown in 
Figure 16.   The second tetracyanoplatinate anion containing Pt2 does not coordinate 
uranium, but is present for charge balance and is involved in the formation of the pseudo 
one-dimensional stacks.   
 Each uranium center is coordinated by three tetracyanoplatinate anions and in turn, 
each tridentate tetracyanoplatinate anion coordinates three U(IV) centers. An oxo bridge 
spans the U(IV) centers on the ladder structural features, thus forming the second 
dimension of the sheet.  This forms a series of parallel ridges and furrows in conjunction 
with a macrostructure like a corrugated sheet.  This structure does contain pseudo one-
dimensional tetracyanoplatinate chains, as shown in Figure 16, which is common with 
square planar cyanometallate complexes.  In the pseudo one-dimensional chains, there 
are two crystallographically independent Pt
?
Pt distances, 3.266(1) and 3.493(1) ?.  
These chains are described in the earlier literature as linear and non-equidistant with Pt 
 42 
atoms forming a x-y-y-x type structure. In this structure, x = a free Pt(CN)
4
2-
 anion and y 
= a complexed Pt(CN)
4
2-
 anion.
19
  This type of chain structure is also described 
previously as linear non-equidistant, and it is often associated with partially oxidized 
systems.
19
  The coordinating tetracyanoplatinate anions coordinate the uranium centers 
through three different U-1
A&E ond angles 172.3(15), 165.2(12), and 155.3(12)?.  The 
U-OH
2
 bonds range from 2.456(1) to 2.514(1) ?.  The U-O
oxo
 bond is 2.0706(7) ? and 
the three U-N bonds range from 2.543(1) to 2.565(1) ?.  
 
 
Figure 16 Packing diagram of (U4) showing the 2-D structural motif and the one-
dimensional linear nonequidistant Pt
...
Pt chains along the c axis.
7
 
 43 
{Th
2
(H
2
O)
10
(OH)
2
[Pd(CN)
4
]
3
}?8H
2
O  (Th5) 
The key feature of the structure of Th5 is a series of one-dimensional chains of 
{Th
2
(OH)
2
(H
2
O)(Pd(CN)
4
)
3
}. There is one crystallographically independent Th
4+
 center 
with a coordination number of nine, and it is best described geometrically as a tricapped 
trigonal prism. Three monodentate tetracyanopalladate anions and six oxygens coordinate  
the  Th
4+
 metal center.  Five of the coordinating oxygens are from water molecules, and 
the other two are from bridging hydroxides.  Two hydroxide ions link the two Th
4+
 sites 
together, and do not form bonds of equal length.  The inversion symmetry is shown in 
two unique Th-OH bond distances of 2.337(3) and 2.371(3) ?.    Two Th
4+
 ions sit 
Figure 17 Projection of {Th
2
(H
2
O)
10
(OH)
2
[Pd(CN)
4
]
3
}?8H
2
O (Th5)  showing the 
pseudo-one dimensional Pd
?
Pd interactions, along the b axis, with the unit cell 
superimposed.  Thorium atoms are labeled in green, oxygen atoms in red, nitrogen atoms 
in blue and palladium atoms in metallic blue.
7
 
 44 
3.9858(4) ? apart from each other, which is a shorter distance than the sum of the Van 
der Waals radii.  The tetracyanopalladate anion bound to the Th
4+
 site extends the chain 
by binding to another asymmetric unit in a cis fashion.
 
The pseudo one-dimensional 
Pd
?
Pd chains are present and can be visualized in Figure 17. Again, chains like these are 
described in the earlier literature as linear and non-equidistant. The two 
crystallographically independent Pd
?
Pd distances are found at 3.2512(5) and 3.4960(9) 
?.  At first glance, the structure of Th2 and Th5 appear very similar as both are 
described as one-dimensional.
9
 Upon closer observation the structure of Th2 can be 
described as a polymeric structure consisting of [-TCPt-Th-(OH)
2
-Th-]
+4
 monomers. 
Inspection of Th5 reveals that the polymeric structure is composed of [-(OH)-Th-
(TCPd)
2
-Th-(OH)-]
+2
  monomers and is not isostructural with Th2.  
 
 
 
 
 
 
 45 
 
 
{(UO
2
)
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]}  (U6) 
The structure of {(UO
2
)
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]} (U6) has one-dimensional bonding 
interactions and consists of extended chains made up of {UO
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]}
 
units. There is one crystallographically independent UO
2
2+
 site.  It has a coordination 
number of seven and is best described as a pentagonal bipyramid.    Each UO
2
2+
 site is 
coordinated by six oxygen atoms and one tetracyanonickelate anion.  Two oxygens are 
from the uranyl oxygen atoms and are found at distances of 1.776(4) and 1.779(4) ? from 
the metal ion.  The second pair of coordinating oxygens are from the DMSO solvent 
molecule, and these are found at 2.380(4) and 2.391(4) ?.   The third pair of coordinating 
oxygens are from the bridging hydroxides and have bond distances of 2.321(4) and 
2.334(4) ?.  One nitrogen from a cis bridging tetracyanonickelate anion also coordinates 
the UO
2
2+
 site.  The structure is extended by two structural features along the one-
Figure 18 Extension of the one-dimensional structure of 
{(UO
2
)
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]} (U6) with the unit cell superimposed.  Uranium 
atoms are labeled in green, oxygen atoms in red, nitrogen atoms in blue and platinum 
atoms in blue metal. Hydrogen atoms are not shown for clarity.
7
 
 46 
dimensional chain; two bridging hydroxides connect uranyl sites and the cis bridging 
tetracyanonickelate anion connects these uranyl sites extending the chain indefinitely.  As 
compared to Th2 and Th5 only a single TCNi unit bonds each UO
2
2+
 center. The 
polymeric structure of U6 is clearly seen in Figure 18 consisting of [-(OH)-UO
2
-TCNi-
UO
2
-(OH)-] monomers. The monomer of U6 resembles the monomer of Th5. In contrast, 
3d metallophilicity is not observed, because the one-dimensional chains do not pack in 
such a way that Ni
?
Ni interactions are observed.  The central reason for this is the small, 
hard 3d Ni
2+
 ions do not readily allow for metallophilic interactions.  In addition, the 
inclusion of DMSO prohibits the stacking of TCNi, while by comparison, in Th5, the 
inclusion of H
2
O allows for the TCPd anions to form the pseudo one-dimensional chains.  
 
 
 
 
 
 47 
 
[Th(C
2
H
6
SO)
9
][Pt(CN)
4
]
2
?4H
2
O (Th7) 
The structure of [Th(C
2
H
6
SO)
9
][Pt(CN)
4
]
2
?4H
2
O (Th7) is ionic in nature.  The 
structure is formed by anions of [Pt(CN)
4
]
2-
 and cations of [Th(C
2
H
6
SO)
8
]
4+
.  The Th
4+
 
site is coordinated in a bicapped trigonal prismatic fashion by eight monodentate DMSO 
molecules.  The structure is completed by two uncoordinated tetracyanoplatinate anions 
and four H
2
O molecules. As shown in Figure 19, columns of tetracyanoplatinate ions do 
form but the Pt spacing between tetracyanoplatinate anions are found to be 8.696 ?, too 
long to be considered pseudo one dimensional Pt chains. 
Figure 19 Projection of the ionic structure of [Th(C
2
H
6
SO)
9
][Pt(CN)
4
]
2
?4H
2
O (Th7).  
Thorium atoms are labeled in green, oxygen atoms in red, nitrogen atoms in blue and 
platinum atoms in blue metal. Hydrogen atoms are not shown for clarity.
8
 
 48 
 
[Th(C
2
H
6
SO)][Fe(CN)
6
]?NO
3
 (Th8) 
The structure of [Th(C
2
H
6
SO)
8
][Fe(CN)
6
]
.
NO
3
 (Th8) is molecular in nature.  It is 
composed of a unit of [Fe(CN)
6
]
-3
 and a unit of [Th(C
2
H
6
SO)
8
]
+4
 
to form the 
[(Th(C
2
H
6
SO)
8
)(Fe(CN)
6
]
+
 cation. The structure is charge balanced by the presence of a 
nitrate anion which is not shown in figure 20.  The Th
4+
 site is coordinated in a tricapped 
trigonal prismatic fashion by one nitrogen from the hexacyanoferrate anion and eight 
monodentate DMSO molecules. Because the hexacyanoferrate molecular geometry is 
octahedral and not square planar it does not allow the formation of Fe
?
Fe pseudo one 
dimensional chains as in other compounds in this class.  As shown in Figure 20, a 
Figure 20 Projection of the structure of [Th(C
2
H
6
SO)
8
][Fe(CN)
6
]?NO
3
 (Th8).  Thorium 
atoms are labeled in green, oxygen atoms in red, nitrogen atoms in blue and iron atoms in 
blue metal. Hydrogen atoms and nitrate anions are not shown for clarity.
8
 
 49 
nitrogen from the hexacyanoferrate ion covalently binds the thorium center with a bond 
length of 2.674 ? which is probably better described as a dative interaction.
39,41
 50 
Table 2 
 
Formula 
Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O 
Th1 
Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O 
Th2 
K
3
[(UO
2
)
2
(OH)(Pt(CN)
4
)
2
]
2
?NO
3
?1.5H
2
O 
U3 
Formula mass 1136.65 1665.85 2517.15 
Color Yellow Green Yellow Green Yellow 
Crystal system Orthorhombic Monoclinic Tetragonal 
Space group Pbca C2/c P4/mbm 
a (?) 13.2464(6) 16.4915(4) 22.1073(2) 
b (?) 20.5599(10) 12.1941(4) 22.1073(2) 
c (?) 22.4536(11 19.5380(5) 12.6202(2) 

.?  90 90 90 
? 90 114.016(4) 90 
?  90 90 90 
V (?
3
) 6115.1(5) 3588.9(2) 6167.9(1) 
Z 8 4 4 
T (K) 193 (2) 295 (2) 290 (2) 
c  0.71073 0.71073 0.71073 
PP
-1
) 14.053 19.989 19.75 
Reflections collected 59819 32269 26733 
Unique reflections 7574 5166 3423 
Rint 0.0737 0.0281 0.0564 
R
1
 >,!
1,@  0.0301 0.0141 0.0522 
wR
2
 (all data)  0.0781 0.0244 0.01562 
  
 51 
Table 3  
Formula 
 
{U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O 
U4 
{Th
2
(H
2
O)
10
(OH)
2
[Pd(CN)
4
]
3
}?8H
2
O 
Th5 
{(UO
2
)
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]}  
U6 
Formula mass 1613.57 1415.52 2094.72 
Color Emerald green Colorless Yellow 
Crystal 
system Triclinic Triclinic Monoclinic 
Space group P
?  P
?  C2/c 
a (?) 9.716 (4) 9.6141 (6) 21.5224(11) 
b (?) 9.823 (4) 9.9479 (6) 10.2531(5) 
c (?) 9.926 (4) 11.1360 (7) 13.3170(6) 

.?  74.191 (7) 73.7480 (10) 90 
? 70.734 (7) 78.0950 (10) 111.9430(10) 
?  67.242 (7) 68.6530 (10) 90 
V (?
3
) 813.2 (6) 945.82 (10) 2725.8(2) 
Z 1 1 2 
T (K) 183 (2) 183 (2) 183 (2) 
c  0.71073 0.71073 0.71073 
PP
-1
) 22.857 9.315 2.552 
Reflections  
collected 7998 9619 10040 
Unique  
reflections 3940 4604 3358 
Rint 0.0582 0.0270 0.0292 
R
1
 >,!
1,@  0.0669 0.0282 0.0298 
wR
2
 (all data)  0.1681 0.0715 0.0746 
 52 
Table 4 
Formula 
[Th(C
2
H
6
SO)
9
][Pt(CN)
4
]
2
?4H
2
O  
Th7 
[Th(C
2
H
6
SO)
8
][Fe(CN)
6
]?NO
3
  
Th8 
Formula mass 3066.60 1131.13 
Color colorless colorless 
Crystal system Triclinic Monoclinic 
Space group P
?  P2
1
n 
a (?) 12.4199(6) 11.9796(9) 
b (?) 20.3265(10) 17.7389(13) 
c (?) 21.1132(10) 20.0389(15) 

.?  102.080(1) 90 
? 98.2710(1) 90.117(2) 
?  96.694(01) 90 
V (?
3
) 5098.25(4) 4258.4(6) 
Z 4 4 
T (K) 183 (2) 183 (2) 
c  0.71073 0.71073 
PP
-1
) 8.803 4.276 
Reflections collected 25422 10600 
Unique reflections 15375 8144 
Rint 0.0579 0.0690 
R
1
 >,!
1,@  0.0585 0.0840 
wR
2
 (all data)  0.1402 0.2164 
 
 53 
Crystallographic Overview 
 A brief review of the structural characteristics of these complexes is presented 
here in an attempt to aid in the discussion of all eight compounds (Th1, Th2, U3, U4, 
Th5, U6, Th7, and Th8) in the following chapters.  Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O (Th1) is 
composed of monomers, [Th(H
2
O)
7
(Pt(CN)
4
)
2
]. The Th
4+
 metal center is bound by two 
monodentate tetracyanoplatinate anions.  These monomers are not covalently bonded to 
another monomer, subsequently, the structural motif is best described as zero-
dimensional.  The formation of pseudo one-dimensional Pt
?
Pt chains is observed from 
the stacking of the monomers.  There are two Pt
?
Pt R values found at 3.3712(2) and 
3.3515(2) ?.  Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O  (Th2) is composed of 
[Th
2
(H
2
O)
10
(OH)
2
(Pt(CN)
4
)
3
] chains, and is best described as one-dimensional. Each 
Th
4+
 metal center is bound by two tetracyanoplatinate anions via two different modes of 
coordination, mono- and bidentate.  The bidentate tetracyanoplatinate anion covalently 
extends the global structure in chains along one dimension.  These chains pack in a way 
that formation of pseudo one-dimensional Pt
?
Pt chains is observed.  The Pt atoms in the 
pseudo one-dimensional chains are spaced equidistant at 3.272(2) ?.  The three-
dimensional structure of (U3) is composed of [UO
2
(OH)(Pt(CN)
4
)
4
] units.  Each UO
2
2+
 is 
bound by four tetradentate tetracyanoplatinate anions.  The tetradentate 
tetracyanoplatinate anions extend the global structure in all three dimensions.  The 
packing of this structure only allows the formation of Pt
?
Pt dimers, found at 3.221(1) ?.
9
  
The two dimensional structure of {U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O  (U4) is composed of  
[U(H
2
O)
5
(O)(Pt(CN)
4
)] units.    The structure contains two crystallographically 
independent types of tetracyanometallate anions: one form binds three U
IV
 centers and 
 54 
the other form is incorporated into the structure for charge balance.  Pt
?
Pt interactions 
are found in this structure at 3.266(1) and 3.493(1) ?.    The one dimensional structure of 
{Th
2
(H
2
O)
10
(OH)
2
[Pd(CN)
4
]
3
}?8H
2
O  (Th5) is composed of one-dimensional chains of 
{Th
2
(OH)
2
(H
2
O)(Pd(CN)
4
)
3
}. These one dimensional chains line up so that the 
tetracyanopalladate ions form Pd
?
Pd interactions found at 3.2512(5) and 3.4960(9) ?.  
The one dimensional structure of {(UO
2
)
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]}  (U6) is composed 
{UO
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]} units. The structure is extended by two structural 
features along the one-dimensional chain; two bridging hydroxides connect uranyl sites 
and the cis bridging tetracyanonickelate anion connects these uranyl sites extending the 
chain indefinitely.  The ionic structure of [Th(C
2
H
6
SO)
9
][Pt(CN)
4
]
2
?4H
2
O (Th7) is zero 
dimensional and the simplest and possible least interesting in regards to the structural 
properties of all eight of these compounds. A thorium center is coordinated by eight 
monodentate DMSO molecules bound through the oxygen atom and the tetrapositive 
charge on the thorium atom is charge balanced by two tetracyanoplatinate anions. 
Chemically it is interesting to note that the DMSO molecules must have a higher affinity 
to the thorium center than the cyanide group from the tetracyanoplatinate. The ionic 
structure of [Th(C
2
H
6
SO)
8
][Fe(CN)
6
]?NO
3
 (Th8) is zero dimensional in nature and 
composed of the simple hexacyanoferrate bound via one cyanide group to the hepta 
DMSO coordinated thorium metal with a nitrate ion included for charge balance.      
In summary, eight cyano bridged 5d-5f complexes Th1, Th2, U3, U4, Th5, U6, 
Th7, and Th8 have been synthesized. These complexes represent the first d
8
 metal 
cyanides coordinated to actinide metals.  The thorough structure elucidation and analysis 
starts to establish An-N-C bonding parameters.  Complexes Th1 and Th2 contain long 
 55 
range Pt-Pt interactions manifested in the quasi one dimensional chains, while complex 
U3 lacks this long range order.  Incorporation of the solvent DMSO into the structures 
negatively impacts the formation of the square planar d
8 
metal interactions.  The synthesis 
of Th1, Th2, and Th5 provides a readily available way to access the Th-N bond without 
having to prepare the thorium starting material as the halide salt, or as an organometallic 
starting material Cp, or Cp*.
39-43
 7KH FRPELQHG SUHSDUDWLRQ VLPSOLFLW\ 7K?1 ERQG
accessibility at bench top conditions, ambient  atmospheric conditions, and in the 
presence of H
2
O is unique in the field of actinide chemistry.  
 
  
 56 
 
 
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2010. 
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Uranium 1996: World Inventories, Capabilities, and Policies; Stockholm International 
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Commun. (Camb) 2010, 46, 4944. 
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K.; Sessler, J. L. Inorg. Chem. (Washington, DC, U. S.) 2007, 46, 5143. 
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2007, 26, 2623. 
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6425. 
 (35) Maynard, B. A.; Smith, P. A.; Sykora, R. E. Acta Crystallogr., Sect. E: 
Struct. Rep. Online 2009, 65, m1132. 
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1543. 
 (37) Holzapfel, W.; Yersin, H.; Gliemann, G. Z. Kristallogr. 1981, 157, 47. 
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Chem., Int. Ed. 2007, 46, 8043. 
 (39) Schelter, E. J.; Morris, D. E.; Scott, B. L.; Kiplinger, J. L. Chem. Commun. 
(Cambridge, U. K.) 2007, 1029. 
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4682. 
 
 
 
 59 
Chapter 3: Emission and Raman Spectroscopy of the Actinide 
Tetracyanometallates 
 
In chapter 2, the solid state structural elucidation of the actinide 
tetracyanoplatinate compounds was discussed in detail.  Figures from chapter 2 have 
been included along with the spectra to help coordinate the features observed in the 
spectra with the structural features.   As with any coordination compound, the structural 
features found from the single crystal x-ray diffraction experiment dictate what can be 
observed via other solid state experimental methods (i.e. photoluminescence and Raman 
spectroscopy).   Chapter 3 will focus on these two experimentation methods with an 
emphasis of pointing out why the observations can be made when considering the 
structural features. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 60 
Excitation and Emission 
 
CRAIC Microspectrophotometer 
As shown in Figure 21 the single crystal samples of Th1 are luminescent when 
excited with ultraviolet radiation.  This was first observed on the bench top using a 
standard ultraviolet (UV) lamp (425 nm).  The CRAIC microspectrophotometer now 
allows for a single crystal sample to be used for fluorescence and UV experiments.  A 
single crystal sample can be mounted on a goniometer head to undergo a structural 
analysis via X-ray diffraction, with the same mounted crystal later placed on a sample 
slide for observation under the microspectrophotometer and then the Raman 
spectrophotometer.  This experimental configuration allows for exact determination of 
Figure 21 Single crystal sample of Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O (TH1), on the left the 
sample is viewed under a magnification of x10.  The same single crystal sample is 
viewed on the right  under a magnification of x10 and 365 nm excitation with the CRAIC 
microspectrophotometer.   
 61 
 
the structural features and one to one correspondence with the observed spectral features.   
 
Thermo NanoDrop Fluorimeter 
At first, the emission characterization was done on a Thermo NanoDrop 
Fluorimeter. The emission spectra of Th1 (Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O), Th2 
(Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O), U3 (K
3
[(UO
2
)
2
(OH)(Pt(CN)
4
)
2
]
2
?NO
3
?1.5H
2
O)  and 
starting materials (K
2
[Pt(CN)
4
]?3H
2
O,UO
2
(NO
3
)
2
?6H
2
O and Th(NO
3
)
4
?6H
2
O) are shown 
in Figure 22. The emission of U3 and the Th(NO
3
)
4
?6H
2
O  are on the same order of 
magnitude as the background. The UO
2
(NO
3
)
2
?6H
2
O emission spectrum is characteristic 
of that salt.
1
 The emission of the K
2
[Pt(CN)
4
] ?3H
2
O starting material shows a broad peak 
centered at 440 nm;
2
 however, both Th1 and Th2 fluoresce further into the visible region. 
Both thorium compounds have broad-band emission, red shifted by about 40 nm for Th1 
0
50000
100000
150000
200000
250000
411 461 511 561 611 661
Wavelength (nm)
R
el
ati
v
e 
F
l
u
o
r
es
cen
ce
 
U
n
i
ts
 
(R
F
U
)
UO2(NO3)2.6H2O
Th(NO3)4.6H2O
K2[Pt(CN)4].3H2O
Th1
Th2
U3
Figure 22 Emission spectra of starting materials, Th1, Th2 and U3 excited at 400 nm.  
The emission of U3 and thorium nitrate are so weak as to be at background levels, as 
seen by the inset in the upper right hand corner which is presented with a y-axis 
magnification of x2000. 
 
 62 
and 90 nm for Th2, relative to K
2
[Pt(CN)
4
]?3H
2
O. Since Th
4+
 is a known non-emitting 
ion, we can assign the broad band emission from Th1 and Th2 as originating from the 
TCPt portions of the structures.
3
   The dominant electronic form of thorium is the 
tetrapositive Th
4+
 species which contains a 5f 
0 
configuration.
4
 All of the electrons are 
spin paired in this electronic state and emission is not expected. The broad emission 
features in both Th1 and Th2 are very unusual for a Th
4+ 
complex and can be assigned to 
a charge transfer state within the tetracyanoplatinate ion since the Th
4+
 ion is non-
fluorescent. On the other hand, the complete lack of observed emission in U3 is rather 
intriguing since both of the starting materials, K
2
[Pt(CN)
4
]?3H
2
O  and UO
2
(NO
3
)
2
?6H
2
O, 
have strong emission when excited at 400 nm.  
 
Photon Technology International spectrometer 
The photoluminescence spectra were collected using a Photon Technology International 
spectrometer (model QM-7/SE). The system uses a high intensity xenon source for 
excitation. Selection of excitation and emission wavelengths are conducted by means of 
computer controlled, autocalibrated ?QuadraScopic? monochromators and are equipped 
with aberration corrected emission and excitation optics. Signal detection is 
accomplished with a photomultiplier tube detector (Hamamatsu model 928) that can 
work either in analog or digital (photon counting) modes. The instrument operation, data 
collection, and handling were all controlled using the FeliX32 fluorescence spectroscopic 
package. UV-vis absorption data was acquired using a Craic Technologies 20/20 PV UV-
visible microspectrophotometer. All of the spectroscopic experiments were conducted on 
neat crystalline samples held in sealed quartz capillary tubes at room temperature. 
 63 
 
 
 
 To try to further extend our characterization of these actinide tetracyanoplatinate 
compounds, photoluminescence measurements were performed to give insight into the 
excitation species.   Th1 and Th2 have the most compelling absorption/emission 
properties.  An example of the contrast upon excitation of the neat, solid samples with 
ambient or 365 nm radiation is shown in Figure 21. The excitation spectra of 
K
2
[Pt(CN)
4
]?3H
2
O can be characterized by the large band at 385 nm which corresponds 
to a charge transfer state,  on the TCPt anion, and the broadband emission feature at 425 
nm is the relaxation of this excited charge transfer state.
5
  Broad band excitation features 
are found in all three spectra; however, since it is known that the dominant form of 
thorium will be the Th
4+
 species, and thus, all electrons will be spin paired in the 
electronic ground state, the excitation spectrum does not originate from the Th
4+
 site.
6
 
This broad band excitation can be attributed to the charge transfer state on the [Pt(CN)
4
]
2-
 
250 300 350 400 450 500 550
R
e
l
at
i
ve
 
F
l
u
or
e
s
c
e
n
c
e
 
U
n
i
t
s
 
Wavelength (nm) 
Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O 
Emission
Excitation
Figure 23  Excitation spectrum of Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O in blue was monitored 
at a wavelength of 487 nm and the emission spectrum in pink was excited at  370 nm.  
 
 64 
anion, which is what would be expected from the tetracyanoplatinate class of compounds 
featuring the Pt
?
Pt one-dimensional columns. Of note in a compound that contains a 
filled valence shell are the low energy features found at 400, 425 and 440 nm in the 
excitation spectrum of Th1 (Figure 23).  It is likely that these features can be attributed to 
vibronic coupling as only one electronic transition is reported for Th
4+
 in this energy 
range, the 6d to 7s transition around 432 nm,
6
 which does not match with these observed 
bands. 
 
 
 
Figure 24  Excitation spectrum of Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O in blue was 
monitored at a wavelength of 480 nm and the emission spectrum in red was excited at  
370 nm. 
 
A correlation has been described in previous works that the separation of the Pt 
sites in the pseudo one-dimensional chains directly corresponds to the emission 
wavelength.
7
  It states that the shorter the distance, R, between the Pt
?
Pt sites within the 
250 300 350 400 450 500 550
R
e
l
at
i
ve
 
F
l
u
or
e
s
c
e
n
c
e
 
U
n
i
t
s
 
Wavelength (nm) 
Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O 
Excitation
Emission
 65 
chain, the lower the energy emission. The Th1 and Th2 compounds appear to follow this 
trend. The shortest Pt
?
Pt spacings in Th1 and Th2 are 3.3515(2) and 3.272(2) ? 
UHVSHFWLYHO\ZLWKWKH
max
 of Th2 UHGVKLIWHGE\aQPDVFRPSDUHGWRWKH
max
 of Th1;
8
 
however, since Th
4+
 should not have excitation, and thus should not be emissive, the 
thorium sites of Th1 and Th2 seem to only function to adjust the Pt
?
Pt distance in these 
compounds. While there is a difference between the excitation profiles of the starting 
material, K
2
[Pt(CN)
4
]?3H
2
O, as compared to Th1 and Th2, the emission profiles can be 
characterized as the same and resultant of the relaxation of the charge transfer state. 
 
 Spectral features are also observed in the emission spectra (Figure 25) of U4 at  
435, 485, 544, 583, 611, and 707 nm.    These features are weaker in intensity and 
sharper, as can be surmised with emission originating from the U(IV) site,
9,10
 as opposed 
Figure 25  Emission spectra of the K
+
 salts of the d
8
 tetracyanometallates and the 
complexes U4, Th5, and U6. 
 66 
to the charge transfer state on the TCPt anion that has broad intense emission features as 
seen in Figure 23, 24, and 25.  
 
 
 
 
 
 
 
 
Raman Spectroscopy 
 The square planar tetracyanometallate anions are able to adopt several 
coordination modes (i.e. monodentate, trans- or cis-bridging, tri and even tetradentate 
K
2
[Ni(CN)
4
]
.
xH
2
O
K
2
[Pd(CN)
4
]
.
xH
2
O
K
2
[Pt(CN)
4
]
.
3H
2
O
Figure 26 Raman spectra of the K
+
 salts of the d
8
 tetracyanometallates in the CN
?
 
stretching region. 
 67 
bridging) and uncoordinated tetracyanometallate anions can also be incorporated into the 
structure. For the simple potassium salts, A
1g
 and B
1g
 are the two CN vibrational modes 
expected in the cyanide stretching region between 2100 and 2300 cm
-1
.  The A
1g
 is more 
intense and has a larger Raman shift as compared to the B
1g
. Our values correlate well 
with data reported as seen in Table 5.
11-13
  The assignment of the observed Raman shifts 
in our compounds is made easier if the square planar cyanometallates are considered as 
maintaining D
4h 
symmetry in the solid state.  In this report, we have chosen to focus on 
the cyanide region. 
Raman spectroscopy was performed using the 514 nm line (20 mW) from an air-cooled 
Argon ion laser (model 163-C42, Spectra-Physics Lasers, Inc.) as the excitation source. 
Raman spectra were collected and analyzed using a Renishaw inVia Raman microscope 
system.  All of the spectroscopic experiments were conducted on neat crystalline samples 
held in sealed quartz capillary tubes at room temperature. 
 
Table 5 Vibrational modes of the d
8
 cyanometallate K
+
 salts given in cm
-1
. 
Assignment K
2
[Ni(CN)
4
]?H
2
O K
2
[Pd(CN)
4
]?H
2
O K
2
[Pt(CN)
4
]?3H
2
O 
v(CN)A
1g
 2132 (2132)
13
 2159 (2150)
12
 2164 (2168)
11
 
v(CN)B
1g
 2125 (2128)
13
 2146 (2139)
12
 2143 (2149)
11
 
 
 68 
  
   Little has been reported previously about thorium compounds and identifiable 
features of Raman spectroscopy, and we wanted to further characterize these using the 
Raman features of these compounds.  The compound Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O (Th1) 
has two unique cyanide environments.  One cyanide environment is only coordinated to 
the Pt center and the other cyanide environment is coordinated to both the platinum and 
thorium metal center.  As compared to the starting material, the peak height ratio of the 
A
1g
 and B
1g 
is altered, and the Raman shifts are larger. The B
1g 
band blue
 
shifts ~13 cm
-1
 
while the A
1g
 band
 
blue
 
shifts ~20 cm
-1
. Although the Th-N bonds in the 
Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O compound, (2.552(5) and 2.571(4) ?) are longer than other 
reported Th-N bonds,
14,15
 the blue shift in the A
1g
 and B
1g 
bands of Figure 27 indicate 
electron density withdrawal from the N lone pair.
16,17
 
Th1
Th2
K
2
[Pt(CN)
4
]
.
3H
2
O
Figure 27  Raman data of Th
x
[Pt(CN)
4
]
y
 compounds and the K
2
[Pt(CN)
4
]?3H
2
O 
starting material. 
 69 
In the next thorium cyanoplatinate compound, Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O 
(Th2),  there are two cyanide environments.  One cyanide environment is coordinated to 
only the platinum center, while the other center is linked to both the platinum center and 
thorium center.  This second environment is located trans to another such environment. 
As compared to Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O (Th1), the 
Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O (Th2) Raman spectra have more features, and the 
features are blue shifted to a greater degree. The B
1g 
band appears at 2160 cm
-1
, this peak 
blue shifts roughly ~17 cm
-1
 as compared to the starting material, K
2
[Pt(CN)
4
]?3H
2
O. We 
believe the A
1g
 vibration has been blue shifted ~26 cm
-1
 in agreement with the notion that 
the Th
4+
 withdraws electron density from the N lone pair. Three other spectral bands are 
seen at roughly 2145,  2173, and 2209 cm
-1
 respectively.  
 
Th5
K
2
[Pd(CN)
4
]
.
xH
2
O
Figure 28 Raman spectra of  Th
2
(OH)
2
(H
2
O)
10
[Pd(CN)
4
]
3
?8H
2
O and K
2
[Pd(CN)
4
]?xH
2
O. 
 70 
  In the first Th[Pd(CN)
4
] structure reported, Th
2
(OH)
2
(H
2
O)
10
[Pd(CN)
4
]
3
?8H
2
O, 
like Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O, there are two cyanide environments.  One 
cyanide environment is coordinated to only the palladium center, while the other 
environment is linked to both the palladium center and the thorium center.  This second 
environment is located cis to another such environment.  In good agreement with the 
Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O compound a total of five spectral features are seen 
(Figure 28) with the same peak trends.   The B
1g 
band appears at 2162 cm
-1
, this peak 
blue shifts roughly ~16 cm
-1
 as compared to the K
2
[Pt(CN)
4
] starting material.  We 
believe the A
1g
 vibration has been blue shifted ~32 cm
-1
, found at 2191 cm
-1
, and this 
would be in agreement with the notion that the Th
4+
 withdraws electron density from the 
N lone pair. Three other spectral bands are seen at roughly 2147, 2174, and 2210 cm
-1
, 
respectively.  
U4
K
2
[Pt(CN)
4
]
.
3H
2
O
Figure 29 Raman spectrum of {U
2
(H
2
O)
10
(O)][Pt(CN)
4
]
3
}?4H
2
O.   
 71 
 In the first U(IV)[Pt(CN)
4
] structure reported,({U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O) 
(U6) there are three cyanide environments. The first cyanide environment is coordinated 
to only the platinum atom, the second cyanide environment is coordinated to both the 
platinum atom and the uranium (IV) center and is trans to another identical environment,  
and the third cyanide environment is coordinated to both the platinum and the uranium 
(IV) center and is trans to the cyanide environment coordinated to only the platinum 
metal.    
DFT Analysis 
Eletronic structure calculations were perfomed, to give insight into the vibrational 
frequencies resulting from the An-NC-M bonding interactions in these actinide 
cyanometallate compounds, using the unrestricted B3LYP hybrid density functional 
theory (DFT)
18,19
 in the Gaussian 09 code.
20
   The Th and U were modeled with the 
Stuttgart relativistic effective core potential and basis set
21-23
 with the C and H atoms 
modeled using a Pople style double-9 6-31++G* basis set with polarization function 
optimized for heavy atoms.
24,25
 The proper f electron configurations, based on 
experimental results, were used for the appropriate ion.  For calculations involving the 
Th
4+
  and the UO
2
2+
 ion this corresponds to a f 
0
 electron configuration. For calculations 
involving the U
+4
 ion a f 
2
 electron configuration was employed. Calculations were 
carried out using the spin-XQUHVWULFWHGIRUPDOLVPZLWK
.VSLQVLQH[FHVVRIVSLQV7 he 
simplest, full unit was assembled using the crystallographic information files from the 
reported Th1, Th2, U3, and U4 compounds.
26,27
  It is important to note that the CIF files 
for structure Th1, Th2, U3, and U4 were manipulated and the calculated structure is a 
pruned version of the CIF file.  These pruned versions of the molecules were used to 
 72 
simplify the gas phase calculations.  For example the U4 structure contains a U(IV) 
center coordinated by 8 water molecules and a single nitrogen from a tetracyanoplatinate 
anion as compared to the solid state structure that is coordinated by 6 water molecules 
and 3 nitrogens from 3 tetracyanoplatinate anions. Using the lowest calculated energy 
from different multiplicities a geometry optimization was performed to alleviate any solid 
state crystallographic strain in the molecule.  
   
Table 6  Single point energy calculations performed using the unrestricted B3LYP 
functional in Gaussian09 revB.01.  Energy given in Hartree-Fock units. 
Job Multiplicity E (HF) 
?(+)  
Th1 1 -2688.102335 0.000000 
Th1 3 -2688.044021 -0.000778712 
Th1 5 -2687.945887 -4.979E-09 
Th1 7 -2687.629621 0.000307 
Th1 9 -2757.039314 -2.24973E-06 
U(Th1) 1 -2757.262479 -4.00424E-05 
U(Th1) 3 -2757.327569 -0.000074 
U(Th1) 5 -2757.318271 -0.000030 
U(Th1) 7 -2757.219955 -1.65928E-06 
U1(Th1) 9 -2757.039314 -0.000002 
      
Th2 1 -3586.11963 -2.32893E-06 
Th2 3 -3585.775907 -2.8973E-06 
Th2 5 -3585.726351 -3.22697E-06 
 73 
Th2 7 -3585.581883 1.12344E-07 
Th2 9 -3585.412239 -0.000004 
U(Th2) 1 -3724.119042 -0.000216 
U(Th2) 3 -3585.775907 -6.94523E-07 
U(Th2) 5 -3585.726452 -0.000014 
U(Th2) 7 -3585.581837 0.000002 
U(Th2) 9 -3585.412239 -0.000003 
      
U3 1 -1500.363653 -2.60991E-06 
U3 3 -1500.332201 -0.000002 
U3 5 -1500.211464 -4.00184E-06 
U3 7 -1500.030710 -9.11421E-07 
U3 9 -1499.797249 -0.000012 
      
U4 1 -1578.415620 -0.000062 
U4 3 -1578.495487 -0.000002 
U4 5 -1578.490605 -0.000006 
U4 7 -1578.334771 -0.000050 
U4 9 -1578.132857 -0.000002 
Th(U4) 1 -1509.244857 -3.9408E-08 
Th(U4) 3 -1509.217155 -6.00242E-07 
Th(U4) 5 -1509.073826 -9.28127E-06 
Th(U4) 7 -1508.856842 -4.39347E-07 
 74 
Th(U4) 9 -1508.639400 -0.000215098 
 
 
Figure 30 Projections of the atom positions from jobs run in Gaussian. The 
crystallographic information files were used as a starting point for atom positions. 
 
 
 
 
Discussion 
Emission 
An earlier paper reports (Capelin 1970) the luminescent detection of metal ions 
including the limit of detection, 20 ppm, for the Th
4+ 
metal ion.
28
 The mode of 
characterization is described as ultraviolet examination with the emission characterization 
results for the white Th
4+
 precipitate given as green.  The precipitate is formed under 
 75 
basic conditions by the addition of NH
3
.  The ThTCPt compounds that we reported 
formed greenish-yellow crystals, and when irradiated with UV light gave a green 
emission (Figure 21).  We attempted to grow ThTCPt crystals at higher pH, but the 
formation of Th(OH)
4 
prevented this.  For these reasons, we do not believe that the 
compounds we reported and the compounds from this much earlier report are the same.
28
      
The lack of intense charge transfer emission in both the uranyl compound 
previously characterized, K
3
[(UO
2
)
2
(OH)(Pt(CN)
4
)
2
]
2
?NO
3
?1.5H
2
O  (U3),
8
 and the U(IV) 
compound reported here, {U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O (U4), is curious. The pseudo 
one-dimensional Pt
?
Pt chains are not present in U3, only dimeric interactions are found 
at 3.2214(15) ?. Both the K
2
[Pt(CN)
4
]?3H
2
O and UO
2
(NO
3
)
2
?6H
2
O starting materials 
emit in the visible range, and it is odd that the product of these two materials is not 
emissive.  Because U3 lacks the long range Pt
?
Pt interactions, the lack of intense charge 
transfer emission seen from U4 may be of more interest as it contains the pseudo one-
dimension chains with R spacings of 3.266(1) and 3.493(1) ?   Further, any electronic 
energy transfer quenching should be forbidden as the TCPt does not change its 
multiplicity upon going from the ground state to the lowest excited state.
29
  
The lack of emission in Th5 and U6 is expected.  The Pd
?
Pd pseudo one-
dimensional structural feature is not linked to the same metal-to-ligand charge transfer 
visible emission as its 5d Pt
?
Pt counterpart.  The formation of pseudo one dimensional 
Ni
?
Ni interactions in the covalently bound  TCNi class of compounds does not appear 
previously in the literature. However these structural interactions do exist in the ionic 
compounds with longer Ni?Ni interactions found at 3.567(2), 3.804(1), and 3.733(1) for 
the strontium, rubidium, and sodium [Ni(CN)
4
]
2-
 salts.
30
 The inclusion of DMSO may 
 76 
play a role in the lack of Ni???Ni interactions, but it is not solely responsible.  The lack of 
these interactions is probably due to the smaller, harder nature of the 3d Ni atom as 
compared to the larger, softer nature of the corresponding 4d and 5d Pd and Pt atoms.     
Raman Spectroscopy 
Table 7 
 
Few reports exist with Raman spectroscopy and structural data to accompany it 
involving TCNi interested in the mode of bridging of the TCNi anion.
31-35
 Within these 
reports, only one structure is characterized as a cis or trans bridging structure
31
, and the 
rest involve the square planar TCNi that is either unbound or all nitrogens bind a metal 
and the D
4h
 symmetry is roughly preserved. In all of these reports, only a single A
1g
 and 
B
1g
 vibration are reported in the cyanide region. We report all the peaks present in the 
&1UHJLRQRIWKH5DPDQVSHFWUDDQGEHOLHYHWKH y correlate to the mode of binding of the 
d
8
 tetracyanometallate, thus originating from the binding of the actinide metal. To our 
knowledge, there are no single crystal structural reports containing covalently bound 
metals to TCPd or TCPt with Raman data to accompany it, making comparing 
assignments with other work a moot point.  This is not to say that structural elucidation of 
the tetracyanometallate ions, and their ionic complexes, have not been reported 
previously, or that Raman spectroscopy has not been performed in separate reports.
11-13
     
Compound  B
1g
    A
1g
   Mode 
Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O  2146vw  2156w   2185s   monodentate 
Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O 2141w 2160m 2173w 2189m 2209m 
bidentate 
K
3
[(UO
2
)
2
(OH)(Pt(CN)
4
)
2
]
2
?NO
3
?1.5H
2
O    2143s    2164s   tetradentate 
{U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O   2146w 2167m   2191s   
uncoordinated 
tridentate 
{Th
2
(OH)
2
(H
2
O)
10
[Pd(CN)
4
]
3
}?8H
2
O   
2142w 2161m 2174w 2189s 2210m 
uncoordinated 
bidentate 
{(UO
2
)
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]}    2138w   2161m   bidentate 
 77 
However, the blue shift of the Raman bands does correlate well with other cyanide 
bridged 4f and 5f and transition metal complexes.
16,17
  
At first glance, the different actinide metal ions (Th
4+
, U(IV), and UO
2
VI
) appear 
to affect the cyanide region of the Raman data in different ways. The UO
2
2+
 has
 
little to 
no effect on shifting the vibrational modes in the cyanide region.  When a [Pt(CN)
4
]
2-
 
coordinates to a tetra positive uranium site, the cyanide region of the Raman spectrum 
displays a peak at 2192 cm
-1
, roughly 28 cm
-1
 higher in energy than the A
1g
 vibration in 
the starting material.  The largest difference occurs when a tetracyanometallate anion 
coordinates to a thorium.  This is most likely a structural restriction, but this is hard to 
confirm, as an isostructural series has not as yet been characterized.  In the three 
compounds containing U, as either UO
2
2+
 or U
4+
, there are not any structural trends that 
correspond with the features seen in the Raman spectra.  This makes the spectral features 
hard to elucidate.   
Upon closer inspection, it seems that it is the binding modes, (uncoordinated, 
mono- bi- tri- and tetradentate)  in which the tetracyanometallate anions are incorporated, 
that are responsible for the spectrum in the cyanide region.  A monodentate 
tetracyanometallate, found in Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O, gives rise to three peaks, the 
two typical A
1g
 and B
1g
 peaks are still observed, but a significant third vibration also 
appears at lower frequency. When the tetracyanometallate coordinates the tetra positve 
thorium metal in a bridging, cis or trans, fashion as in, Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O 
and {Th
2
(H
2
O)
10
(OH)
2
[Pd(CN)
4
]
3
}?8H
2
O,   five peaks are seen in the cyanide region of 
the spectrum.  Again, the typical A
1g
 and B
1g
 vibrations are found, but three other 
vibrations are observed at lower frequency. The tridentate bridging species 
 78 
{U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O gives three vibrations in the cyanide stretching region, 
again the A
1g
 and B
1g
 vibrations similar to the potassium salt are found, but a third 
vibration is found at lower frequency.  
In the compounds containing Th
4+
, the similarity of the Raman features in the 
Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O and Th
2
(OH)
2
(H
2
O)
10
[Pd(CN)
4
]
3
?8H
2
O structures is 
remarkable.  In the spectrum of each, there are five spectral features.  Assigning the first 
two spectral features to the B
1g
 and A
1g
 vibrations, respectively, would indicate 
backbonding from the Th metal.  Instead, the B
1g
 and A
1g
 vibrations are assigned to more 
blue shifted spectral features in accordance with a bound metal withdrawing electron 
density form the N lone pair.  The same spectral features are not observed in the 
Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O compound (Th1).  One possible explanation for this is the 
bridging features of the cyanometallate anion observed in the compounds.  In both the 
Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O (Th2) and Th
2
(OH)
2
(H
2
O)
10
[Pd(CN)
4
]
3
?8H
2
O (Th5) 
structures, the cyanometallates coordinate the Th
4+
 centers in a bidentate bridging fashion 
DQG ILYH VSHFWUDO IHDWXUHV DUH REVHUYHG LQ WKH &1 UHJLRQ 7KLV LV LQ FRQWUDVW WR WKH
Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O (Th1) structure in which the coordinating cyanometallate 
only binds iQDPRQRGHQWDWHIDVKLRQDQGWKUHHVSHFWUDOIHDWXUHVDUHREVHUYHGLQWKH&1
region. 
The tetradentate species found in K
3
[(UO
2
)
2
(OH)(Pt(CN)
4
)
2
]
2
?NO
3
?1.5H
2
O  
shows only the A
1g
 and B
1g
 vibrations.  Interesting is that the bridging cyanometallate 
species in {(UO
2
)
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]} show a similar spectrum as 
K
2
[Ni(CN)
4
]?xH
2
O, but the A
1g
 and B
1g
 vibrations are at lower frequency. The Q1 
(UO
2
)
2+
 symmetric stretching vibration is observed at 826 cm
-1
 and correlates well with 
 79 
previous reports.
36,37
 A weakness in characterizing these compounds by Raman 
spectroscopy alone is if the solid state structure contains more than one type of 
tetracyanometallate binding.  With Raman data alone in the cyanide region of the 
spectrum you could only classify the tetracyanometallate mode of binding as tetradentate, 
monodentate-tridentate, and bidentate.  
 
Computational Analysis 
 In the tetracyanoplatinate free anion the A
1g
 vibration corresponds to all four  
cyanide groups stretching and compressing in phase.  The B
1g
 corresponds to two trans 
cyanide groups stretching while the other two trans cyanide groups are compressing. 
Experimental data has shown that there are two stretches in the CN region that 
correspond to the A
1g 
(2164 cm
-1
exp
,
 
2225 cm
-1
cal
) and B
1g
 (2143cm
-1
exp
 2202.05 cm
-1
cal
) 
vibrational modes in the square planar tetracyanoplatinate molecule.  The difference 
between the experimental and calculated A
1g
 and B
1g
 vibrational frequencies seem to 
correlate (A
1g
-B
1gexp 
= 21cm
-1
, and A
1g
-B
1gcal  
= 23 cm
?1
). When the symmetry of the free 
tetracyanoplatinate anion is disturbed by binding a 5f center, more spectral features are 
observed in the experimental data.  This can be visualized if each individual cyanide 
bond has its own environment.  As seen in Table 8 additional vibrational modes are 
calculated when the smallest whole unit is used.  The smallest whole unit is different than 
the crystallographic asymentric unit as symmetry operations are not considered.  Because 
the D
4h
 symmetry is broken with the binding of an actinide metal, confirmed by the 
structural elucidation in chapter 2, this computational data aligns with the observed 
 80 
experimental data. Additional support is given by the calculation of the lone, 
uncoordinated tetracyanoplatinate anion giving only two vibrations. 
 
 
 
Table 8  Vibrational modes calculated by the unrestricted B3LYP functional.  
 
Frequency 
Raman 
Activity 
 
Frequency 
Raman 
Activity 
 
Frequency 
Raman 
Activity 
U4 2103.74 101759.0311 Th1 2177.27 1534.8014 U(Th1) 2151.37 53458.0379 
  2222.04 2599.8266 
 
2191.58 426.6418 
 
2164.68 420128.9835 
  2527.76 9165.9218 
 
2206.36 37.671 
 
2311.63 10164.5883 
  2585.19 13900.2591 
 
2207.63 447.2925 
 
2356.1 40649.9583 
Th(U4) 2036.35 23747.7646 
 
2216.27 1431.607 
 
2387.14 7106.9728 
  2352.23 17668.2092 
 
2224.88 939.9632 
 
2455.58 6568.2785 
  2572.09 16816.6473 
 
2244.67 1115.5023 
 
2462.23 372429.9 
  2634.19 25849.0315   2245.95 2597.1117       
 
Conclusions 
A thorough characterization of the actinide cyanometallates has been presented 
here. In general, the An[CM] class of compounds synthesized and structurally 
characterized during the course of research represents the first time these type of 
complexes with the 5f elements have  been reported in the literature.
26,27
  Solid state 
characterization illustrates the structural novelty of this class of compounds. The most 
outstanding example of this is the Th-NC bond found in Th1, Th2, Th5,and Th8 
represent the total known Th-NC linkages in the Cambridge Crystallographic Database.
38
  
Also interesting are the oxygen (hydroxyl and oxo) bridging species observed in Th2, 
U4, Th5, and U6 are not observed in the analogous 4f, Ln[CM] literature.
39-42
   
 81 
Further experimental techniques were employed to investigate the electronics of 
these An[CN] compounds.  Of note, only the thorium containing compounds (Th1 and 
Th2) gave observable emission in the visible region of the spectra.
27
   Again, this is an 
interesting aspect of these compounds as the Th
4+
 has a completely empty O electron 
shell, thus no electrons are able to be excited and subsequent emission should not be 
observed (CATE Vol. 1, pg 59).
6
  It is important to note that this research does not make 
the claim that the emission from Th1 and Th2 originates from the thorium sites.   Instead, 
the broad band in the excitation spectra of these compounds is attributed to the ligand to 
metal charge transfer band from the cyanide groups bound to the platinum atoms.
5
  The  
packing structure of these compounds in the solid state leads to the observed differences 
in emission between Th1 and Th2.  The observed Pt
?
Pt distances in Th1 are 3.371 and 
3.351 ?, and a single Pt
?
Pt distance is observed in Th2 at 3.272 ?.  The Pt
?
Pt distances 
in Th1 and Th2 differ by roughly 0.010 ? and, correspondingly, WKH
max
 of Th2 is red 
VKLIWHGE\aQPDVFRPSDUHGWRWKH
max
 of Th1.  Effectively, the thorium atoms are 
placeholders, they directly affect the Pt
?
Pt spacings in these two compounds, which 
results in the difference of observed emission in the solid state.
8
  While there is a 
difference between the excitation profiles of the starting material, K
2
[Pt(CN)
4
]?3H
2
O, as 
compared to Th1 and Th2, the emission profiles can be characterized as the same feature 
and resultant of the relaxation of the charge transfer state. 
The lack of observable intense charge transfer bands in the uranyl, U3, containing 
compound and the U(IV), U4, containing compound is confounding at first.  Upon 
looking at the solid state structural features of U3 it is apparent that only dimeric Pt
?
Pt 
interactions found at 3.2214(15) ? are observed.  Effectively, the lack of overlap from 
 82 
?infinite?  d
z
2 
orbitals in the Pt?Pt chains quenches the emission from metal to ligand 
charge transfer bands seen in Th1, Th2, and other previously reported tetracyanoplatinate 
compounds.   The lack of intense charge transfer emission seen from U4 may be of more 
interest as it contains the pseudo one-dimension chains with R spacings of 3.266(1) and 
3.493(1) ?.   Any electronic energy transfer quenching should be forbidden, because the 
TCPt does not change its multiplicity upon going from the ground state to the lowest 
excited state.
29
     The lack of emission in Th5, U6, Th7, and Th8 is expected as the 
actinide metal centers have an empty O electronic shell.
6
  The Pd
?
Pd pseudo one-
dimensional structural feature is not linked in the literature to the same metal-to-ligand 
charge transfer visible emission as its 5d Pt
?
Pt counterpart.
43
  When a covalent bond is 
formed between a cyanide group of a tetracyanonickelate and another metal the formation 
of pseudo one dimensional Ni
?
Ni interactions in the TCNi class of compounds has not 
been observed  previously  in the literature. The inclusion of DMSO may play a role in 
the lack of Ni???Ni interactions in U6 and the lack of Pt?Pt interactions in Th7, but it is 
not solely responsible.  The lack of these interactions is probably due to the smaller, 
harder nature of the 3d Ni atom as compared to the larger, softer nature of the 
corresponding 4d and 5d Pd and Pt atoms.   The octahedral molecular structure of the 
hexacyanoferrate anion forbids packing interaction of Fe
?
Fe atoms.  
Vibrational spectra of the actinide cyanometallates were observed with a confocal 
Raman Microscope.  For the simple potassium tetracyanoplatinate salt, the A
1g
 and B
1g
 
are the two CN vibrational modes expected in the cyanide stretching region between 
2100 and 2300 cm
-1
.  The cyanide region of the spectrum provides the most information 
regarding the solid state structure of these compounds.  Previous reports of other 
 83 
cyanometallates
31-35
  only reported two stretches in this region.  In our spectra, we were 
able to observe multiple stretches in this cyanide region. 
It seems that it is the binding modes, (uncoordinated, mono- bi- tri- and 
tetradentate)  in which the tetracyanometallate anion is incorporated, that are responsible 
for distinct changes in the spectrum in the cyanide region.  A monodentate 
tetracyanometallate, found in Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O, gives rise to three peaks, the 
two typical A
1g
 and B
1g
 peaks are still observed, but a significant third vibration also 
appears at lower frequency.
26
 When the tetracyanometallate coordinates the tetra positve 
thorium metal in a bridging, cis or trans, fashion as in, Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O 
and {Th
2
(H
2
O)
10
(OH)
2
[Pd(CN)
4
]
3
}?8H
2
O,   five peaks are seen in the cyanide region of 
the spectrum.  Again, the typical A
1g
 and B
1g
 vibrations are found, but three other 
vibrations are observed at lower frequency. The tridentate bridging species 
{U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O gives three vibrations in the cyanide stretching region, 
again the A
1g
 and B
1g
 vibrations similar to the potassium salt are found, but a third 
vibration is found at lower frequency.  
Of note in the compounds containing Th
4+
 are the similarity of the Raman 
features in the Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O and Th
2
(OH)
2
(H
2
O)
10
[Pd(CN)
4
]
3
?8H
2
O 
structures.  In the spectrum of each, there are five spectral features.  Assigning the first 
two spectral features to the B
1g
 and A
1g
 vibrations, respectively, would indicate 
backbonding from the Th metal.  Instead, the B
1g
 and A
1g
 vibrations are assigned to more 
blue shifted spectral features in accordance with a bound metal withdrawing electron 
density form the N lone pair.  The same spectral features are not observed in the 
Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O compound (Th1).  One possible explanation for this is the 
 84 
bridging features of the cyanometallate anion observed in the compounds.  In both the 
Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O (Th2) and Th
2
(OH)
2
(H
2
O)
10
[Pd(CN)
4
]
3
?8H
2
O (Th5) 
structures, the cyanometallates coordinate the Th
4+
 centers in a bidentate bridging fashion 
DQG ILYH VSHFWUDO IHDWXUHV DUH REVHUYHG LQ WKH &1 UHJLRQ 7KLV LV LQ FRQWUDVW WR WKH
Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O (Th1) structure in which the coordinating cyanometallate 
only binds in a monodentate fashion and three sSHFWUDOIHDWXUHVDUHREVHUYHGLQWKH&1
region. 
The tetradentate species found in K
3
[(UO
2
)
2
(OH)(Pt(CN)
4
)
2
]
2
?NO
3
?1.5H
2
O  
shows only the A
1g
 and B
1g
 vibrations.  Interesting is that the bridging cyanometallate 
species in {(UO
2
)
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]} show a similar spectrum as 
K
2
[Ni(CN)
4
]?xH
2
O, but the A
1g
 and B
1g
 vibrations are at lower frequency. The Q1 
(UO
2
)
2+
 symmetric stretching vibration is observed at 826 cm
-1
 and correlates well with 
previous reports.
36,37
 A weakness in characterizing these compounds by Raman 
spectroscopy alone is if the solid state structure contains more than one type of 
tetracyanometallate binding.  With Raman data alone in the cyanide region of the 
spectrum, you could only classify the tetracyanometallate mode of binding as 
tetradentate-anionic, monodentate-tridentate, and bidentate.  
The computational analysis of the compounds was done using DFT methods with 
the unrestricted B3LYP hybrid functional. In the actinide cyanometallates, the interesting 
structural features that give rise to the observed electronic properties, arise from the long-
range packing interactions of the Pt
?
Pt interactions.   This is unfortunate because 
defining enough heavy atoms in a calculation was computationally time consuming and 
not practically possible to be carried out during my time at Los Alamos National 
 85 
Laboratory.  What was able to be calculated were the Raman vibrations of the simplest 
actinide cyanometallates.  These calculations involved the appropriate actinide unit, 
including the oxo bridged species, and the full metal cyanides coordinating these units 
along with the coordinated and uncoordinated solvent molecules. The coordinates of the 
atoms for these calculations were directly taken from the crystallographic information 
files of the appropriate compounds (Th1, Th2, U3, U4, Th5 U6). These computational 
analysis provided insight into the growth of vibrational bands in the Raman spectrum.  
Additional bands were seen in the calculated structures as compared to the experimental 
work.  Each of these bands seen in the calculated vibrational spectra corresponds to a 
breaking of the idealized D
4h
 symmetry square planar geometry of the anions.  It can be 
clearly seen in the crystallographic description that the symmetry is broken, however, 
neither earlier reports nor our experimental work were able to observe all of the bands 
predicted by the calculations. 
  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 86 
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 89 
Chapter 4: Synergistic Thorium Mediated Synthesis of  
2,3-diaminophenazine 
 
 
 
 
Scheme 1 Oxidation of ortho-phenylenediamine to 2,3-diaminophenazine. 
 
 
 In the last decade, reports detailing metal mediated synthetic methods
1-4
 or catalysis 
5-8
 
incorporating the use of actinide metals have become more common.  The focal point of 
this research is typically an actinide metal center saddled with sterically hindered ligands 
(such as cyclopentadiene, pentamethylcyclopentadienyl,
7,9
 and N-ethylmethylamine).
7,9
   
Ultimately, the ligand and the metal are bound covalently, to some degree, and the 
electronics of these ligand-actinide complexes and their subsequent reactivity  have not 
been clearly explained. 
7,9
.  
 The heterocycle 2,3-diaminophenazine is thought to play a role in iron-
sequestration in some bacteria, and is of interest for the self-assembly of nanobelts and 
?green? fluorescence sensitive assays.
10
 2,3-diaminophenazine is produced via H
2
O
2
 
catalysis by horseradish peroxidase and fungal laccase enzymes;
11
 non-biological 
synthetic pathways are known including catalysis by Cu(II) and Fe(III).
10,12,13 
 We wanted 
to observe the metal mediation of the unencumbered actinide cations.   Here, we report 
the thorium nitrate, uranyl nitate, and oxygen  mediated synthesis of 2,3-
diaminophenazine. 
 90 
 
Figure 31   Chart depicting the data from table 1.   
  
 As seen in Figure 31, dioxygen alone oxidizes ortho-phenylenediamine to 2,3-
diaminophenazine. Figure 31 also shows  that incorporating the simple actinide nitrate 
salts [Th(NO
3
)
4
 and UO
2
(NO
3
)
4
] enhances the oxidation of ortho-diaminobenzene to 2,3-
diaminophenazine in the presence of dioxygen. While this oxidation occurs at order of 
magnitudes slower than the simple FeCl
3
 salt,
10
 we wanted to investigate this oxidation 
reaction because simple, sterically unencumbered actinide centers are not unusual.  The 
results of the actinide containing reactions are of interest.  It is evident that the addition of 
actinide ions (Th
+4
 and UO
2
2+
) to the aqueous solution provide metal mediation for the 
oxidative generation of 2,3-diaminophenazine.  Increasing the Th
4+
 concentration by a 
factor of 2 increases the formation of the 2,3-diaminophenazine product as seen in Figure 
 91 
31 (Th and Th run 2).  This data appears to indicate  that including the actinide (Th
+4
 or 
UO
2
+2
) ions in the presence of dioxygen examples a synergistic behavior, as the sum of 
the ?O
2
? and degassed ?actinide salt? reactions are less than the isolated product in the 
?Th
+4
 + O
2
? reaction alone. 
 To better understand the influence of dioxygen in the mechanism of the oxidation 
reaction, two reactions were set up to run seven days; the first reaction Schlenk flask was 
degassed to remove as much dioxygen as possible and contained Th(NO
3
)
4
 as the actinide 
source, the second reaction Schlenk flask was also degassed to remove as much dioxygen 
as possible and contained UO
2
(NO
3
)
2
 as the actinide source.  After 7 days, no observable 
precipitate was present in the reaction flask containing Th
+4
,
 
and the solution appeared to 
be the same color as at time 0. No phenazine was detected.The reaction flask with UO
2
+2
 
as the actinide source was found to contain 0.0230 grams of isolable 2,3-
diaminophenazine.  This result appears to indicate that in the presence of oxygen, in the 
form of terminal oxo?s of the uranyl subunit, are needed for the oxidation to occur and 
that the oxo?s from the actinyl units may also be a useful oxygen source in this reaction 
pathway.
9
    
 A third reaction was started to determine whether oxygen was important in the 
role of the reaction scheme.  A Schlenk flask was set up with only a stir bar in an 
aqueous solution of ortho-phenylenediamine.  Argon was bubbled through the solution 
for two hours, and then put through three cycles of freeze-pump-thaw in an effort to 
remove all possible traces of O
2
.  Two reaction attempts have been made to rid the 
Schlenk flask of O
2
, in both instances a 25% yield of 2,3-diaminophenazine has been 
observed.  If these results are found to remain accurate it would give evidence that any 
 92 
oxygen donor will mediate the reaction as this reaction would require the oxygen from 
H
2
O to serve as the oxidant. Interestingly, as this reaction contained only H
2
O and 
ortho-phenylenediamine, a literature search was unable to find any information on the 
temperature induced oxidation of ortho-phenylenediamine in an inert atmosphere.         
 Previous reports in the literature of phenazines prepared in this fashion feature 
metals that are able to go through one electron oxidations (Cu(II)
13 
and Co(II)
14
) and 
SURSRVHG PHFKDQLVPV KDYH LQYROYHG  -dioxygen with hydrogen peroxide evolution. 
This mechanism would be highly unlikely, for either the Th
+4
 or the UO
2
+2 
ions, as both 
metal centers contain complete electronic shells K, L, M and N; also neither ion 
possess paired or unpaired electrons in the O shell.
15
  Further observation of the data in 
the chart of Figure 31 may give some insight into how the reaction proceeds.   If the 
data were examined then the trace of the Th
+4
 (exponential) as compared to the trace of 
the UO
2
+2
 (stepwise) data appear to follow different paths. This may be rationalized if 
the reaction proceeds in two different pathways. 
 93 
 
 
  
 Single crystals of X-ray diffraction quality 2,3-diaminophenazine were grown 
directly from the reaction flasks.  After a reaction had been heated, it was set aside 
undisturbed to cool for two days.  While the structure of 2,3-diaminophenazine is known, 
this structure crystal structure (C
12
H
10
N
4
)
2
 7H
2
O differs from other known reports by the 
number of waters of hydration in the lattice as can be seen in figure 32.   As would be 
H[SHFWHG?
?
?VWDFNLQJLQWHUDFWLRQVDUHIRXQGDWc$OVRLQWHUHVWLQJLQWKHFU\VWDO
structure is the seven member ring formed by the hydrogen bonding of the terminal 
amine groups and a water of hydration.  This may give some insight into how the 
mechanism of the reaction proceeds.   
Figure 32 Projection of the asymmetric unit of (C
12
H
10
N
4
)
2
?7H
2
O. 
 94 
Conclusions 
Fundamentally, these observations engage the idea of using the depleted actinide 
reserve, especially depleted 
238
U, as a source for new routes of metal mediation.     In 
future research we plan to monitor these reactions using a UV-vis spectrometer to more 
precisely document the concentrations of both the ortho-phenylenediamine starting 
material and the 2,3-diaminophenazine  product.   We plan on investigating the electronic 
role of these actinide centers, UO
2
2+
 and Th
4+
, and also if the Np
5+
 and PuO
2
2+
 
can
 
mediate this reaction. It would be very unlikely that these actinide ions go through one 
electron oxidations that have been proposed for other metal centers as this would lead to 
removal of a single electron from a filled shell.  If these metal units go though one 
electron oxidations or reductions then a signal would be evident from the corresponding 
unpaired electron in an electron paramagnetic resonance experiment.   It is tough to argue 
that incorporating actinide ions into reaction pathways can result in green chemistry 
following the principles established by Anastas and Warner.  Yet, these reaction 
conditions do abide by several principles of green chemistry including: mild reaction 
conditions, safer solvents, and catalysis. 
 
 
 
Synthesis 
Typical Reaction:  0.0040 moles of ortho-phenylenediamine was heated at 80? C in a 100 
ml round bottom flask charged with a stir bar and 100 ml of deionized H
2
2:KHQWKH -
phenylenediamine dissolved the appropriate volume of a stock actinide starting material 
solution was added to the mixture to allow a 1:100 stoichiometric ratio.  The reaction was 
 95 
allowed to stir and heat at 80? C for the duration of the experiment.  When the experiment 
time had lapsed; the solution was filtered, the solid was washed with hexanes, and dried 
in a vacuum oven.   The dried material was then scraped from the filter paper and 
weighed.  Mass spectrometry analysis was perfomed on the dried material and a mass of 
211.0961 (M+1) was obtained. 
 96 
 
Table 9 Experiments were run with Th(NO
3
)
4
 and UO
2
(NO
3
)  as the metal mediator.  Ortho-phenylenediamine has been abbreviated 
OPD. 2,3-diaminophenazine has been abbreviated DAP. 
  Temp Time OPD mmol 
Th(NO
3
)
4
 
mmol 
UO
2
(NO
3
)
2
 
mmol DAP mmol % yield DAP/Metal mmol ratio 
Th                 
  80 24 3.997 0.03953   0.03223 1.613 101.1 
  80 50 4.005 0.03973   0.56730 28.33 100.8 
  80 71 4.002 0.03953   0.68057 34.01 101.2 
  80 93 4.003 0.03973   0.81754 40.85 100.8 
  80 122 4.005 0.03953   0.89242 44.57 101.3 
  80 142 3.991 0.04128   0.99763 49.99 96.68 
  80 166 4.003 0.04109   1.15261 57.59 97.43 
                  
  80 24 8.597 0.08973   0.91137 21.20 95.82 
  80 48 8.580 0.09070   1.62085 37.78 94.60 
  80 72 8.591 0.09070   3.25687 75.81 94.72 
  80 96 8.495 0.08857   4.11991 96.99 95.91 
  80 120 8.550 0.09244   3.41517 79.88 92.49 
  80 144 8.537 0.08857   3.92986 92.06 96.39 
Th 
Degassed                 
  80 168 3.990 0.04070   Trace Amount   98.04 
UO
2
                 
  80 25 3.949   0.03953 0.02844 1.440 99.90 
  80 43 3.949   0.03953 0.01137 0.5761 99.90 
  80 66 3.949   0.03953 0.29147 14.76 99.90 
  80 91 3.949   0.03953 0.31659 16.034 99.90 
 97 
  80 116 3.949   0.03953 0.28531 14.45 99.90 
  80 139 3.949   0.03953 0.94550 47.89 99.90 
  80 168 3.949   0.03953 0.92891 47.05 99.90 
UO
2
 
Degassed                 
  80 166 3.990   0.03952 0.10284 5.155 100.0 
No Metal                 
  80 24 3.987     0.02275 1.141   
  80 48 3.987     0.06019 3.019   
  80 71 3.987     0.08768 4.400   
  80 96 3.987     0.29573 14.83   
  80 119 3.987     0.22749 11.41   
  80 168 3.987     0.64218 32.21   
                  
Degassed 80 165 3.989     0.49905 25.02   
 98 
 
References Cited 
 
 (1) Schelter, E. J.; Morris, D. E.; Scott, B. L.; Kiplinger, J. L. Chem. 
Commun. (Cambridge, U. K.) 2007, 1029. 
 (2) Weiss, C. J.; Marks, T. J. Dalton Trans. 2010, 39, 6576. 
 (3) Weiss, C. J.; Wobser, S. D.; Marks, T. J. Organometallics 2010, 29, 6308. 
 (4) Kiplinger, J. L.; Pool, J. A.; Schelter, E. J.; Thompson, J. D.; Scott, B. L.; 
Morris, D. E. Angew. Chem., Int. Ed. 2006, 45, 2036. 
 (5) Hayes, C. E.; Platel, R. H.; Schafer, L. L.; Leznoff, D. B. Organometallics 
2012, 31, 6732. 
 (6) Wobser, S. D.; Marks, T. J. Organometallics 2013, 32, 2517. 
 (7) Barnea, E.; Moradove, D.; Berthet, J.-C.; Ephritikhine, M.; Eisen, M. S. 
Organometallics 2006, 25, 320. 
 (8) Stubbert, B. D.; Marks, T. J. J. Am. Chem. Soc. 2007, 129, 4253. 
 (9) Andrea, T.; Barnea, E.; Eisen, M. S. J. Am. Chem. Soc. 2008, 130, 2454. 
 (10) He, D.; Wu, Y.; Xu, B.-Q. Eur. Polym. J. 2007, 43, 3703. 
 (11) Zhou, P.; Liu, H.; Chen, S.; Lucia, L.; Zhan, H.; Fu, S. Molbank 2011, 
M730. 
 (12) Nemeth, S.; Simandi, L. I.; Argay, G.; Kalman, A. Inorg. Chim. Acta 
1989, 166, 31. 
 (13) Peng, S. M.; Liaw, D. S. Inorg. Chim. Acta 1986, 113, L11. 
 (14) Rosso, N. D.; Szpoganicz, B.; Martell, A. E. Inorg. Chim. Acta 1999, 287, 
193. 
 (15) Morss, L.; Edelstein, N. M.; Fuger, J. The Chemistry of the Actinide and 
Transactinide Elements Springer, 2006; Vol. 1. 
 
 
 
! 99!
Chapter 5:  Synthesis, Isolation, Structural Characterization 
and Emision Spectroscopy of Salzine Compounds 
 
 
 
 
 
 One new 2-(1H-imidazo[4,5-b] phenazin-2-yl)phenol (salzine) derivative has 
been synthesized and the structural elucidation of three novel solid state structures are 
reported in this chapter.  The salzine clas of molecules were reported first in 2011 with 
the several diferent substituents on the benzene ring (X= H, CH
3
O,  CH
2
OH, Br, and 
Cl).
1
  In this report only the synthesis via a Mn
III 
mediated reaction and the solution phase 
UV and fluorescence spectra were reported.  These salzine derivatives offer the common 
five atom ligand geometry (N-C-C-C-O) found in chapter 1 to bind actinide atoms and 
have solid state structural characterization.
2
    
 
 !
Figure 3  Projection of the 2-quinoxalinol salen molecule.!!Atoms as shown are labeled:  
H in white,  O in red, N in blue, and C in grey. 
! 100!
The 2-quinoxolinol salen ligand (salqu) was first synthesized in the Gorden group 
in 2007, and this report included the synthesis of the ligand and other related ligands.
3
  
This ligand system contains two (N-C-C-C-O) structural motifs per molecule.  Yet, only 
structures with a bound uranyl ion have been reported with this 2-quinoxalinol salen 
ligand system.  Until now, the free 2-quinoxalinol salen ligand has only been 
characterized in the solution phase.  The quinoxolinol salen ligand features an  (O-N-N-
O) tetradentate binding pocket, as shown in Figure 33, which can be used in metal 
coordination.  The O32-N3 distance is 2.596(4), the N3-N2 distance is 2.737(6), the N2-
O31 distance is 2.568(4), and the O31-O32 distance is 4.037(5) ?.  Several metals have 
been shown to coordinate to the ligand including; Cu(II), Mn(II), Co(II), Ni
2+
, and 
UO
2
2+
.
4
  The 2-quinoxalinol salen-Cu(II) complexes have been shown to be active 
towards C-H activation and oxidation. The tetradentate O-N-N-O binding pocket of the 
2-quinoxalinol salen ligand coordinates UO
2
+2
 and several solid state structural reports 
were made of this solid state structure with diferent solvents incorporated into the crystal 
lattice.
5
  It was thought that increasing the conjugation of the 2-quinoxalinol with two 
additional aromatic rings, formed from condensation with salicylaldehyde, would 
increase the emision properties of the ligand metal complexes.  Exploring along these 
same lines, it was thought that increasing the conjugation of the backbone by starting 
with 2,3-diaminophenazine,  then subsequent condensation with salicyaldehyde 
derivatives, would provide a larger aromatic scafold system with a O-N-N-O pocket for 
metal binding.  
 
 
! 101!
Synthesis of the benzeimidazole ligands 
 
C
19
H
12
N
4
O Compound Salzine was synthesized by disolving 0.05052 grams of 
2,3-diaminophenazine in 20 ml of salicylaldehyde in a round bottom flask, charged with 
a stir bar.  The reaction was heated at 80 ?C for 24 hours.  The solution changes color 
during the heating phase from red to very dark red/black.  The reaction solution was then 
filtered and washed with ethanol leaving the crude yelow product. 
C
27
H
28
N
4
O Compound t-butsalzine was synthesized by disolving 0.2371 grams 
of 2,3-diaminophenazine in 25 ml of pyridine in a round bottome flask, charged with a 
stir bar.  The reaction was heated at 110 ?C for until al the 2,3-diaminophenazine had 
disolved, then 0.2630 grams of 3,4-ditertbutyl-2-hydroxy benzaldehyde was added.  The 
reaction was heated at 110 ?C for 24 hours.  The reaction solution was then filtered and 
washed with hexane, leaving the crude brown product.  This brown product was pased 
thorugh a silica gel column during column chromatography using ethyl acetate as the 
mobile phase.  The yelow fractions were collected and rotovapped to drynes to recover 
the pure product.    
[UO
2
(C
19
H
11
N
4
O)(DMSO)]?DMSO  complex Usalzine was synthesized by 
disolving 0.0201 grams of salzine in 1 ml of DMSO in a test tube.  This solution was 
then layered with a ethanol solution containing 0.0117 grams of UO
2
(NO
3
)
2
.  This test 
tube was set up for crystal growth in a slow difusion 20 dram vial with hexanes as the 
difusion solvent.  After 4 days quality single crystals were observed and used for X-ray 
difraction.     
 
! 102!
X-ray Difraction 
 !
Scheme 2 Shows the starting materials, 2,3-diaminophenazine and salicyaldehyde the 
product [2-(1H-imidazo[4,5-b]phenazin-2-yl)phenol], and a possible Schif base 
intermediate. 
 Figure 34 of the salzine [2-(1H-imidazo[4,5-b]phenazin-2-yl)phenol] molecule shows 
that a diferent condensation result is observed for the 2,3-diaminophenazine starting 
material as opposed to the 2-quinoxolinol.  As sen in the hyposthesized scheme 2, 
during a condensation event betwen the aldehyde and the amine functional group of 2-
quinoxalinol, a single condensation occurs forming a Schif base.  This leaves the second 
amine site on the 2-quinoxolinol available for another condensation with an aldehyde.  
Figure 33 shows that the reaction does not lead down the same pathway when 2,3-
diaminophenazine provides the amine source.  Instead, it is postulated, that the aldehyde 
and an amine go through a second condensation resulting in the evolution of H
2
O, then 
the lone pair on the remaining amine atacks the imine, forming an imidazole in this 
proces.  Two representative structures were synthesized and isolated as shown  in Figure 
34 and Figure 35.  As sen in Figure 35,  the O1-N2 distance is found at 2.5866 (19) ?. 
In comparison to the two O-N distances of the 2-quinoxolinol salen compound found at 
2.596(4) and 2.568(4) ? the distance is shorter betwen these two atoms. 
! 103!
 
 
!
Figure 34  Projection of the asymetric unit of the salzine molecule.  Atoms as shown are 
labeled:  H in white,  O in red, N in blue, and C in grey. 
 
 
!
Figure 15 Projection of the asymetric unit of tbut-salzine. Atoms as shown are labeled: 
H in white,  O in red, N in blue, and C in grey. 
As sen in Figure 35, the O1-N2 distance is found at 2.5569(18) ? in comparison to the 
two O-N distances of the 2-quinoxolinol salen compound found at 2.596(4) and 2.568(4) 
? the distance is shorter betwen these two atoms. 
! 104!
!
Figure 36  Projection of the asymmetric unit of salzine-UO
2
.  The non-coordinating  
solvent DMSO molecule has been removed for clarity.  Atoms as shown are labeled: H 
in white,  O in red, N in blue, C in grey, and sulfur in yelow. 
!
As sen in Figure 36, the O3-N1 distance is found at 2.767(9) ? in comparison to the  O-
N distance of the salzine ligand found at 2.5866(19) ?.  Clearly, upon binding of this 
bidentate O-N binding site, the O-N distance expands to acommodate the metal.  The 
uranium center is seven coordinate and shown to have a beautiful symmetrical pentagonal 
bipyramidal geometry.  These seven sites are coordinated by six oxygen atoms and one 
nitrogen atom.  Two terminal oxo atoms of the UO
2
+2
 unit acount for two of the six 
oxygen atoms.  Three addition oxygen atoms can be acounted for by the coordination of 
a DMSO solvent molecule and an acetate anion.  The remaining oxygen and nitrogen 
atoms that fil the coordination sphere of the uranium are from the salzine ligand.   The 
U-N distance is observed at 2.558(6) ?.  The U-O distance is found at 2.220(6) ?. 
 
! 105!
CRAIC Microspectrophotometer 
!
!
Figure 37 Transmision and emision spectra of the salzine ligand.  The image in the 
upper right corner is at a magnification of x10 and shows the sample this data was taken 
from.  
The transmision and emision spectra of the salzine ligand were obtained by 
taking the single crystal used in the structural elucidation and directly putting it onto a 
quartz slide for further characterization with the CRAIC microspectrophotometer.  As 
sen in Figure 37  there are two dominate spectral features sen in the emision spectra of 
the salzine compound.  The emision resulting from an excitation at 280 nm results in a 
featureles spectrum.  The emision resulting from an excitation wavelength of 365 nm 
results in a broad band feature centering around 605 nm.  The emision resulting from an 
excitation wavelength of 546 nm results in a shoulder centered around the same 605 nm 
region.   
 
200 300 400 500 600 700 800 
R
e
l
ati
ve
 U
n
i
ts
 
Wavelength (nm) 
Transmission 
280 nm 
365 nm 
546 nm 
! 106!
!
Figure 38  Transmision and emision spectra of the salzine-UO
2
 complex.   
The transmision and emision spectra of the salzine-UO
2
 complex were obtained 
by taking the single crystal used in the structural elucidation and directly putting it onto a 
quartz slide for further characterization with the CRAIC microspectrophotometer.  As 
sen in Figure 38, and in comparison to Figure 38,  there are two dominate spectral 
features sen in the emision spectra of the salpen-UO
2
 complex.  In contrast to just the 
salzine ligand, a spectral feature is observed from the 280 nm excitation at 362 nm with a 
shoulder observed at 328 nm. The emision resulting from an excitation wavelength of 
365 nm results in a broad shoulder feature around 365 nm.  The emision resulting from 
an excitation wavelength of 546 nm results is featureles.   The growth of spectral 
features in the salzine-UO
2
 complex in both the transmision and 280 nm excitation 
spectra are ways to tel if the ligand has bound the UO
2
 center in the solid state.  Curious 
200 300 400 500 600 700 800 
R
e
l
ati
ve
 U
n
i
ts
 
Wavelength nm 
transmission 
280 nm 
365 nm 
546 nm 
! 107!
is the loss of the large, broad band excitation feature found in the 365 nm emision 
spectrum of the salzine ligand.   
!
Figure 39 Transmision and emision spectra of the tbut-salzine.  The image in the upper 
right corner is at a magnification of x10 and shows the sample this data was taken from. 
The transmision and emision spectra of the tbut-salzine ligand were obtained by 
taking the single crystal used in the structural elucidation and directly putting it onto a 
quartz slide for further characterization with the CRAIC microspectrophotometer.    
There are no spectral features sen in the emision spectra of the salpen compound. This 
is a result worth investigating further as comparison with salzine in Figure 37 some 
emision features would be expected.  Unfortunately, a metal complex with the tbutyl-
salzine ligand has not been isolated yet so no comparison can be made in the solid state 
of the electronic properties. 
! 108!
!
Figure 40  Transmision and emision spectra of  2-quinoxalinol salen.  The image in the 
upper right corner is at a magnification of x10 and shows the sample this data was taken 
from. 
 
!
!
The transmision and emision spectra of the 2-quinoxalinol ligand were obtained 
by taking the single crystal used in the structural elucidation and directly putting it onto a 
quartz slide for further characterization with the CRAIC microspectrophotometer.  As 
sen in Figure 40 there are no spectral features sen in the emision spectra of the 2-
quinoxalinol salen compound. This is a result worth further investigation in comparison 
with the solution phase UV-vis data of just the 2-quinoxalinol salen ligand and the 2-
quinoxalinol salen-UO
2
 complex.   
200 300 400 500 600 700 800 
R
e
l
ati
ve
 U
n
i
ts
 
Wavelength nm 
transmission 
256 nm 
365 nm 
546 nm 
! 109!
Synthesizing additional ligands with this common five atom (N-C-C-C-O) ligand 
geometry is worthy of note as several other solid state structures over the last decade 
have included the structural motif when coordinating to an actinide center.
2
 Also, in 
future work, the 2-quinoxalinol salen-UO
2
 single crystal should be regrown. Comparing 
the solid state spectra of the 2-quinoxolinol salen ligand with that of the UO
2
 complexed 
2-quinoxalinol structure with the CRAIC microspectrophotometer may give valuable 
insight into the electronics of the metal-ligand interactions.   
!
!
!
! !
! 110!
 
References Cited 
 
 (1) Lei, Y.; Li, D.; Ouyang, J.; Shi, J. Adv. Mater. Res. (Durnten-Zurich, 
Switz.) 2011, 311-313, 1286. 
 (2) Gorden, A. E. V.; DeVore, M. A.; Maynard, B. A. Inorg. Chem. 
(Washington, DC, U. S.), Ahead of Print. 
 (3) Wu, X.; Gorden, A. E. V. J. Comb. Chem. 2007, 9, 601. 
 (4) Wu, X. G.; Hubbard, H. K.; Tate, B. K.; Gorden, A. E. V. Polyhedron 
2009, 28, 360. 
 (5) Wu, X. H.; Bharara, M. S.; Bray, T. H.; Tate, B. K.; Gorden, A. E. V. 
Inorg. Chim. Acta 2009, 362, 1847. 
 
 
!
! 111!
Chapter 6: Conclusions and Future Work 
 
 
Actinide Cyanometallates 
  The ThTCPt compounds, Th1 and Th2, are unique among the reported thorium 
literature, because we believe they are the first reported Th(IV) containing compounds to 
have both emision and structural work reported. The metal cation acts as a placeholder 
that tunes the R-value betwen Pt centers in the pseudo one-dimensional chains. Th5 
extends the set of reported, solid state thorium isocyanide complexes to a total of three.  
Mono- bi- and tridentate bridging TCM?s, where M = Pt or Pd, has been shown in the 
solid state to give a fingerprint in the CN region of the Raman spectrum.  The 
computational analysis performed using the unrestricted b3lyp functional gave valuable 
insight into the vibrational frequencies observed in the Raman spectrum of these 
compounds.  This work lends support to the hypothesis that the spectral features sen in 
the experimental work are related to the incorporation mode of the tetracyanoplatinate 
anion (un-, mono-, bi-, tri-, and/or ter-dentate); however, when more than one 
tetracyanoplatinate anion binds a 5f center, asigning the spectral features become les 
clear.   
A reasonable conclusion from this computational analysis is that coordination of 
an actinide metal center breaks the symmetry of the D
4h
 cyanometalate anion and this 
leads to an increased number of vibrational stretches in the cyanide region.  These 
vibrational modes may not have been observed in the experimental work because the 
sensitivity of the instrument.  Unfortunately, we were unable to synthesize an 
An
x
[Ni(CN)
4
]
y
 analog in aqueous solution, and the DMSO incorporated into U6 prohibits 
! 112!
the formation of more peaks in the cyanide region of the Raman spectrum. Previous 
literature has only reported two vibrations, A
1g
 and B
1g
, in the 2000 cm
-1
 region. We 
report on one molecular unit and three bridging compounds that have more than two 
vibrations in this region of the Raman spectrum.  This wil provide valuable structural 
information when single crystal XRD analysis is not possible.   
 
 
Future Work 
 
Actinide cyanometallates 
Furthering the work in the actinide cyanometalate clas of compounds wil 
require synthesizing new compounds, containing transuranic elements.  Multiple 
reactions have been atempted using an aqueous solution of Np(V)O
2
Cl and these 
atempts resulted in the formation of a black non-crystaline solid precipitate probably a 
result of the reduction potential of Pt(II) [Pt
II
 + 2e
-
 > Pt
(s)
,  E
o
 = +1.18 V].
1
 Two possible 
avenues to further pursue with the transuranic elements are available; first would be to 
use a cyanometalate with a lower reduction potential, K
2
[Ni(CN)
4
] or K
2
[Pd(CN)
4
],  and 
second would be to use a diferent solvent (DMSO, DMF, DMA, ?) to reduce the 
possibility of  reducing the metal from the cyanometalate.   Also, transition metal 
cyanides were purchased to be studied in these complexes (Zn(CN)
2
, Pt(II)(CN)
2
, 
Cu(I)CN, K
3
[Co(CN)
6
], K
3
[Fe(CN)
6
], and K
4
[Fe(CN)
6
]).  In aqueous solution they 
precipitated out as microcrystaline products and were never characterized.  Using a polar 
organic solvent (such as DMSO, DMA, or DMF) may provide the environment needed  
! 113!
to properly crystalize the material in X-ray difraction quality samples.  The most 
interesting compounds may come from the solvent DMA.  DMA is a planar, polar, 
organic solvent which may alow for platinophilic stacking interactions to be observed.   
 
Oxidation of ortho-phenylenediamine 
 A flaw in the reporting of the isolated yield of the oxidation of ortho-
phenylenediamine is the method in which it is obtained.  Difering amounts of product 
are lost in the filtering steps for each reaction,  making the results qualitative, but hardly 
quantitative.  To improve these results UV-vis should be employed to get acurate 
measurements of the concentration of ortho-phenylendiamine when the reaction starts 
and when the reaction has completed.  Further, it should be sen if the reaction can go to 
completion and what the most eficient mediation loading could be.  Dioxygen is thought 
to play an important role in the reaction pathway, to explore this the dioxygen presure 
can be increased using a Parr bomb.   Future eforts should also focus on atempting to 
use other benzene derivatives, with ortho amine and alcohol functional groups, to prepare 
larger ring systems from diferent starting materials.  Two examples of these starting 
materials would be 2-aminophenol and 1,2-dihydroxybenzene. Simple combinatorial 
enumeration [possible molecules = 2
N
] would need to be done to figure amount the 
number of possible product molecules available when N number of diferent starting 
materials are available.  
 
 
 
! 114!
Salzine  
 The salzine project has a huge potential for expansion by a future researcher.  The 
most important facet of synthesizing these reactions is that the salicylaldehyde needs to 
be soluble in the reaction solvent.  Pyridine sems to be an optimum solvent for the 
reaction, les optimal for the researcher considering the health implications by acidental 
exposure.  When 2,3-diaminophenazine is used as the starting backbone, so far, only the 
monosubstituted imidazole has been observed, as sen in chapter 5.  One aspect of a more 
careful synthetic researcher would be to try to isolate the disubstituted compound.  This 
may not be possible under the current reaction conditions.  Also, using diferent 
benzaldehyde starting materials can increase the number of diferent salzine molecules.  
A search of commericialy available materials shows several options: 2-hydroxy-5-nitro-
benzaldehyde, 3-tert-butyl-2-hydroxybenzaldehyde, 5-chloro-2-hydroxybenzaldehyde, 3-
bromo-5-chloro-2-hydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,3-
dihydroxybenzaldehyde, and 2-hydroxy-5-methylbenzaldehyde.   One metal complex has 
been isolated, salpen-UO
2
. Further salzine complexes need to be synthesized, isolated, 
and characterized.  Several other metals can be used for example: VO
2+
, Cu (I), Cu (II), 
Cu (III), Ce(IV), Gd
3+
, Th+4, U(IV), U(VI), NpO
2
+
, and PuO
2
2+
.
 
    
Using these newly synthesized salzine molecules, synthesized from the 
hydroxybenzaldehydes listed above, and the metals available it should be a possibility to 
isolate these metal complexes.  When the complexes have been isolated it should be 
atempted to grow single crystals.  The most succesful method to this point in 
crystalizing out the salen/salzine complexes has been slow difusion.  Slow evaporation 
has been useful in obtaining single crystals from a pure source of ligand.  When single 
! 115!
crystals have been isolated structure elucidation using the X-ray difractometer should be 
used.  The single crystals can then be put through a series of spectrometer methods using 
the Craic microspectrophotometer to understand the electronic properties.  Further, the 
electrochemical properties should be characterized using cyclic voltametry.  This will 
give insight into the bonding interaction betwen the ligand and the metal. 
 
Phenazineimidazole  
Another possible avenue for exploration is reaction of 2,3-diaminophenazine with glycine 
under 4 N HCl at reflux.  This has been reported to give a glycine benzimidazole in 
previous work with ortho-phenylenediamine.
2
 This reaction should produce the glycine 
phenazineimidazole, as sen in scheme 3, with the amine group available for 
condensation with a dicarboxylic acid to produce a new series of molecules with large 
sections of aromaticity and several hard and soft donor binding sites.  This proposed 
molecule can be sen in the following reaction scheme 4.  It may be just as interesting to 
start with the 2-quinoxalinol diamine, make the imidazole via addition of 4 N HCl and 
follow with the condensation with 2,6-pyridinedicarboxylic acid.  The reason why this 
 Scheme 3  Reaction of 2,3-diaminophenazine with glycine under 4 N HCl conditions and 
reflux should produce the phenazineimidazole product which can be used in further 
synthetic steps. 
! 116!
may be more interesting is that the 2-quinoxalinol has orders of magnitude higher 
emision when excited via a simple UV lamp.  
 
Scheme 4 Starting with the phenazineimidazole starting material. 
!
The same synthetic methods can be employed as with the salzine project.  Al the 
amino acids can be used as starting material in place of glycine.  This creates a large 
array of ligands possible for coordination with the typical metals:  VO
2+
, Cu (I), Cu (II), 
Cu (III), Ce(IV
)
, Gd
3+
, Th
4+
, U(IV), UO
2
2+
, U
VI
, NpO
2
+
, and PuO
2
2+
.  Using these newly 
synthesized salzine molecules, synthesized from the hydroxybenzaldehydes listed above,  
and the phenazineimidazoles and the metals available it should be a possibility to isolate 
these metal complexes.  Also the stoichiometry betwen the metal and the salzine ligands 
should be explored as a 2:1 salzine metal complex would be expected and can be 
visualized in Figure 41 and Figure 42.  When the complexes have been isolated it should 
be atempted to grow single crystals.  The most succesful method to this point in 
crystalizing out the salen/salzine complexes has been slow difusion.  Slow evaporation 
has been useful in obtaining single crystals from a pure source of ligand.  When single 
crystals have been isolated structure elucidation using the X-ray difractometer should be 
! 117!
used.  The single crystals can then be put through a series of spectrometer methods using 
the Craic microspectrophotometer to understand the electrochemical properties.  Further, 
the electrochemical properties should be characterized using cyclic voltametry.  This 
wil give insight into the bonding interaction betwen the ligand and the metal. 
!
!
Figure 41 Possible 2:1 salzine metal complex. 
!
Figure 42  Possible 1:1 phenezeneimidazole metal complex. 
!
! !
! 118!
!
References Cited 
 
! (1)! Housecroft,!C.;!Sharpe,!A.!Inorganic)Chemistry;!Pearson!Education!
Limited,!207;!Vol.!3.!Pg.!1022.!
! (2)! Tyagi,!N.;!Mathur,!P.!Spectrochim.)Acta,)Part)A!2012,!96,!759.!
 
 
!
! 119!
Appendix 1: Crystalographic Tables 
 
 
 
 
 
 
Crystallographic Data Collection for  Th1, Th2, and U3 
 
 
Crystals of compounds 2 and 3 were obtained in good yield from slow evaporation in 
water at room temperature. Crystals of 1 were obtained by slow evaporation of a water 
solution with a pH of 2.5. X-ray difraction data for 1 were collected at -80 ?C on a 
Bruker SMART APEX CCD X-ray difractometer unit using Mo K? radiation from 
crystals mounted in Paratone-N oil on glas fibers. SMART (v 5.624) was used for 
preliminary determination of cel constants and data collection control. Determination of 
integrated intensities and global cel refinement were performed with the Bruker SAINT 
Software package using a narrow-frame integration algorithm. X-ray data for 2 and 3 
were collected using a Varian Oxford Xcalibur E single-crystal X-ray difractometer. 
Intensity measurements were performed using Mo K? radiation, from a sealed-tube 
Enhance X-ray source, and an Eos area detector. CrysAlis
R1
 was used for preliminary 
determination of the cel constants, data collection strategy, and for data collection 
control. Following data collection, CrysAlis was also used to integrate the reflection 
intensities, apply an absorption correction to the data, and perform a global cel 
refinement. The program suite SHELXTL (v 5.1) was used for space group 
determination, structure solution, and refinement.
1
 Refinement was performed against F
2
 
by weighted full-matrix least square, and empirical absorption correction (SADABS
2
) 
was applied. H atoms were found from the diference fourier maps. 
! 129!
U4, Th5,  U6, Th7, Th8, salzine, Usalzine, and t-butsalzine 
The X-ray difraction datasets were collected at 183 K, on a Bruker SMART APEX CCD 
X-ray difractometer unit using Mo K? radiation, from crystals mounted in Paratone-N 
oil on glas fibers. SMART (v 5.624) was used for preliminary determination of cel 
constants and data collection control. Determination of integrated intensities and global 
cel refinement were performed with the Bruker SAINT software package using a 
narrow-frame integration algorithm.  The program suite SHELXTL (v 5.1) was used for 
space group determination, structure solution, and refinement.
3
 Refinement was 
performed against F
2
 by weighted full-matrix least squares, and empirical absorption 
correction (SADABS) was applied. Hydrogen atoms for U6 were found from the 
diference fourier maps. Projections were generated in the Olex2.1-1 graphics program.
4
 
Table 1 contains key results of the X-ray experiments and additional crystalographic 
information is included as Supporting Information. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
! 130!
Crystallographic Table 1.   
Crystal data and structure refinement for Th1, Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O. 
 
Identification code     Th1 
Empirical Formula     C
8
 H
34
 N
8
 O
17
 Pt
2
 Th 
Formula weight     1136.65 
Temperature      193(2) K 
Wavelength      0.71071 
Crystal System     Orthorhombic 
Spacegroup      Pbca 
Unit cel dimensions      
       a = 13.2464(6) ?    ? =    90.0 ? 
       b = 20.5599(10) ?     ? =    90.0 ?  
       c = 22.4536(11) ?    ? =    90.0 ? 
Volume      6115.1(5) ?
 3 
 
Z       8 
Calculated density     2.469 Mg/m
3 
Absorption coeficient    14.053 mm
-1
 
F(000)      4160 
Crystal size                          0.80 x 0.80 x 0.09 mm 
Theta range for data collection      1.81 to 28.27 ?   
Limiting indices                      -17<=h<=17,-27<=k<=2729<=l<=29 
Reflections collected / unique       59819 / 7574 [R(int) = 0.0737]  
Completenes to theta = 28.27        99.9 %  
Absorption correction                Analytical 
Max. and min. transmision           0.3710 and 0.0314 
Refinement method                   Full-matrix least squares on F
2
 
Data / restraints / parameters       7574 / 0 / 313 
Goodnes-of-fit on F
2
               0.999 
Final R indices [I>2sigma(I)]        R1 = 0.0301, wR2 = 0.0766 
R indices (al data)                  R1 = 0.0373, wR2 = 0.0781 
Largest dif. peak and hole          2.154 and -3.034 e. ?
-3
 
  
! 131!
Crystallographic Table 2.  Atomic coordinates ( x 10
4
) and equivalent isotropic 
displacement parameters (?
2
x 10
3
) Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O.  U(eq) is defined as 
one third of the trace of the orthogonalized U
ij
 tensor. 
________________________________________________________________________ 
 x y z U(eq) 
________________________________________________________________________ 
Th(1) 3617(1) 3956(1) 8669(1) 14(1) 
Pt(1) 3747(1) 6259(1) 7345(1) 16(1) 
O(1) 2519(3) 3947(2) 7783(2) 28(1) 
N(1) 3683(3) 5121(2) 8278(2) 22(1) 
C(1) 3711(4) 5557(2) 7954(2) 18(1) 
O(2) 4947(3) 3941(2) 7922(2) 25(1) 
Pt(2) 3733(1) 1421(1) 7668(1) 15(1) 
N(2) 1312(3) 2367(3) 8310(3) 33(1) 
C(2) 3733(4) 6956(3) 7957(3) 21(1) 
O(3) 2275(3) 3225(2) 9036(2) 23(1) 
N(3) 6121(4) 2301(2) 8688(2) 31(1) 
C(3) 3809(4) 6923(3) 6703(3) 24(1) 
O(4) 2058(3) 4602(2) 8865(2) 25(1) 
N(4) 3619(4) 5162(3) 6382(2) 35(1) 
C(4) 3683(4) 5561(3) 6732(3) 26(1) 
O(5) 5104(3) 4559(2) 9052(2) 25(1) 
N(5) 3705(3) 2874(2) 8098(2) 18(1) 
C(5) 3725(4) 2356(3) 7925(2) 18(1) 
O(6) 4743(3) 3181(2) 9197(2) 24(1) 
N(6) 3954(4) 1798(3) 6321(2) 33(1) 
C(6) 3872(4) 1663(3) 6813(3) 22(1) 
O(7) 3459(3) 4136(2) 9730(2) 27(1) 
C(7) 3567(4) 1168(3) 8520(3) 20(1) 
N(7) 3449(4) 1006(2) 9002(2) 31(1) 
O(8) 127(3) 4252(2) 8998(2) 32(1) 
N(8) 6239(3) 4929(3) 7635(2) 28(1) 
C(8) 3755(4) 487(3) 7462(2) 21(1) 
O(9) 4100(4) 2602(2) 10200(2) 36(1) 
O(10) 4764(3) 3339(2) 6865(2) 30(1) 
O(11) 4819(3) 1362(2) 9962(2) 38(1) 
! 132!
O(12) 6790(3) 3788(2) 177(2) 35(1) 
O(13) 2101(3) 4223(2) 5978(2) 32(1) 
O(14) 5082(3) 5813(2) 9419(2) 28(1) 
O(15) 2691(3) 3258(2) 6760(2) 30(1) 
O(16) 2020(4) 2537(2) 10071(2) 38(1) 
O(17) 1751(4) 4061(3) 10301(3) 74(2) 
  
! 133!
Crystallographic Table 3.   Bond lengths [?] and angles [?] for 
Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O. 
_____________________________________________________ 
Th(1)-O(7)  2.420(4) 
Th(1)-O(2)  2.434(4) 
Th(1)-O(1)  2.464(4) 
Th(1)-O(3)  2.469(4) 
Th(1)-O(5)  2.481(4) 
Th(1)-O(6)  2.485(4) 
Th(1)-O(4)  2.494(4) 
Th(1)-N(1)  2.552(5) 
Th(1)-N(5)  2.570(4) 
Pt(1)-C(2)  1.985(6) 
Pt(1)-C(3)  1.986(6) 
Pt(1)-C(1)  1.990(6) 
Pt(1)-C(4)  1.991(6) 
N(1)-C(1)  1.155(7) 
Pt(2)-C(8)  1.975(6) 
Pt(2)-C(6)  1.991(6) 
Pt(2)-C(7)  1.995(6) 
Pt(2)-C(5)  2.007(6) 
N(2)-C(2)#1  1.160(8) 
C(2)-N(2)#2  1.160(8) 
N(3)-C(3)#3  1.176(8) 
C(3)-N(3)#4  1.176(8) 
N(4)-C(4)  1.139(8) 
N(5)-C(5)  1.135(7) 
N(6)-C(6)  1.146(7) 
C(7)-N(7)  1.142(8) 
N(8)-C(8)#4  1.168(8) 
C(8)-N(8)#3  1.168(8) 
 
O(7)-Th(1)-O(2) 138.02(13) 
O(7)-Th(1)-O(1) 138.15(13) 
O(2)-Th(1)-O(1) 82.58(15) 
O(7)-Th(1)-O(3) 72.68(13) 
! 134!
O(2)-Th(1)-O(3) 138.01(13) 
O(1)-Th(1)-O(3) 80.77(13) 
O(7)-Th(1)-O(5) 69.61(14) 
O(2)-Th(1)-O(5) 70.74(14) 
O(1)-Th(1)-O(5) 138.78(14) 
O(3)-Th(1)-O(5) 139.48(14) 
O(7)-Th(1)-O(6) 71.35(13) 
O(2)-Th(1)-O(6) 83.43(13) 
O(1)-Th(1)-O(6) 137.26(12) 
O(3)-Th(1)-O(6) 83.24(13) 
O(5)-Th(1)-O(6) 71.25(13) 
O(7)-Th(1)-O(4) 70.93(13) 
O(2)-Th(1)-O(4) 136.75(13) 
O(1)-Th(1)-O(4) 70.01(13) 
O(3)-Th(1)-O(4) 70.69(12) 
O(5)-Th(1)-O(4) 109.29(13) 
O(6)-Th(1)-O(4) 138.98(13) 
O(7)-Th(1)-N(1) 101.46(15) 
O(2)-Th(1)-N(1) 75.52(14) 
O(1)-Th(1)-N(1) 75.52(14) 
O(3)-Th(1)-N(1) 135.31(13) 
O(5)-Th(1)-N(1) 67.86(14) 
O(6)-Th(1)-N(1) 138.21(13) 
O(4)-Th(1)-N(1) 65.79(13) 
O(7)-Th(1)-N(5) 128.82(15) 
O(2)-Th(1)-N(5) 67.17(13) 
O(1)-Th(1)-N(5) 67.51(13) 
O(3)-Th(1)-N(5) 70.85(13) 
O(5)-Th(1)-N(5) 124.67(13) 
O(6)-Th(1)-N(5) 69.82(13) 
O(4)-Th(1)-N(5) 125.91(13) 
N(1)-Th(1)-N(5) 129.71(15) 
C(2)-Pt(1)-C(3) 90.4(2) 
C(2)-Pt(1)-C(1) 92.6(2) 
C(3)-Pt(1)-C(1) 176.8(2) 
C(2)-Pt(1)-C(4) 177.0(2) 
! 135!
C(3)-Pt(1)-C(4) 89.8(2) 
C(1)-Pt(1)-C(4) 87.2(2) 
C(1)-N(1)-Th(1) 161.2(4) 
N(1)-C(1)-Pt(1) 175.5(5) 
C(8)-Pt(2)-C(6) 90.9(2) 
C(8)-Pt(2)-C(7) 88.5(2) 
C(6)-Pt(2)-C(7) 178.8(2) 
C(8)-Pt(2)-C(5) 176.8(2) 
C(6)-Pt(2)-C(5) 92.2(2) 
C(7)-Pt(2)-C(5) 88.5(2) 
N(2)#2-C(2)-Pt(1) 177.5(5) 
N(3)#4-C(3)-Pt(1) 177.1(5) 
N(4)-C(4)-Pt(1) 178.1(5) 
C(5)-N(5)-Th(1) 170.1(4) 
N(5)-C(5)-Pt(2) 176.4(5) 
N(6)-C(6)-Pt(2) 179.5(6) 
N(7)-C(7)-Pt(2) 177.6(5) 
N(8)#3-C(8)-Pt(2) 177.1(5) 
_____________________________________________________________ 
Symmetry transformations used to generate equivalent atoms: 
#1 -x+1/2,y-1/2,z    #2 -x+1/2,y+1/2,z    #3 -x+1,y-1/2,-z+3/2  
#4 -x+1,y+1/2,-z+3/2  
! 136!
Crystallographic Table 4.   Anisotropic displacement parameters (?
2
x 10
3
) for 
Th(H
2
O)
7
[Pt(CN)
4
]
2
?10H
2
O.  The anisotropic displacement factor exponent takes the 
form: -2?
2
[ h
2
a*
2
U
11
 + ... + 2 h k a* b* U
12
 ] 
________________________________________________________________________ 
 U
11
 U
22
 U
33
 U
23
 U
13
 U
12
 
________________________________________________________________________ 
Th(1) 18(1)  14(1) 10(1)  0(1) 0(1)  0(1) 
Pt(1) 19(1)  16(1) 14(1)  2(1) 1(1)  0(1) 
O(1) 38(2)  26(2) 19(2)  -3(2) -8(2)  6(2) 
N(1) 27(3)  18(2) 20(3)  2(2) -2(2)  -1(2) 
C(1) 24(3)  16(3) 14(3)  -4(2) 0(2)  0(2) 
O(2) 36(2)  24(2) 16(2)  -2(2) 10(2)  -3(2) 
Pt(2) 19(1)  15(1) 13(1)  -2(1) 1(1)  0(1) 
N(2) 31(3)  30(3) 38(3)  -8(3) 3(2) -1(2) 
C(2) 21(3)  19(3) 23(3)  -1(2) 0(2)  -1(2) 
O(3) 24(2)  24(2) 19(2)  -1(2) 3(2)  -6(2) 
N(3) 35(3)  30(3) 29(3)  -9(2) 3(2)  0(2) 
C(3) 25(3)  21(3) 25(3)  -1(2) 0(2)  0(2) 
O(4) 23(2)  24(2) 27(2)  2(2) 5(2)  5(2) 
N(4) 47(3)  36(3) 21(3)  -7(2) -4(2)  0(2) 
C(4) 35(3)  26(3) 16(3)  9(2) 0(2)  -1(2) 
O(5) 26(2)  27(2) 23(2)  -3(2) -6(2)  -3(2) 
N(5) 26(2)  15(2) 13(2)  -2(2) 2(2)  -1(2) 
C(5) 16(3)  25(3) 13(3)  4(2) 1(2)  0(2) 
O(6) 31(2)  24(2) 16(2)  1(2) -1(2)  6(2) 
N(6) 40(3)  39(3) 21(3)  0(2) 3(3)  -4(2) 
C(6) 24(3)  23(3) 18(3)  -6(2) 0(2)  0(2) 
O(7) 26(2)  42(2) 12(2)  -3(2) 2(2)  -1(2) 
C(7) 22(3)  18(3) 19(3)  -4(2) 1(2)  -3(2) 
N(7) 43(3)  27(3) 24(3)  2(2) 3(2)  -6(2) 
O(8) 31(2)  31(2) 35(3)  -2(2) -1(2)  -1(2) 
N(8) 32(3)  20(3) 32(3)  4(2) 5(2)  -1(2) 
C(8) 28(3)  23(3) 11(3)  -3(2) 4(2)  0(2) 
O(9) 56(3)  35(2) 16(2)  1(2) 4(2)  -1(2) 
O(10) 37(2)  32(2) 21(2)  -2(2) 0(2)  1(2) 
O(11) 45(3)  41(3) 28(3)  -1(2) -6(2)  4(2) 
! 137!
O(12) 36(2)  40(3) 28(3)  1(2) 0(2)  4(2) 
O(13) 30(2)  36(2) 29(3)  -3(2) -4(2)  -2(2) 
O(14) 37(2)  29(2) 18(2)  -6(2) -4(2)  -3(2) 
O(15) 39(2)  30(2) 21(2)  -2(2) -3(2)  -1(2) 
O(16) 58(3)  36(2) 20(2)  7(2) 6(2)  -1(2) 
O(17) 44(3)  139(6) 40(3)  -45(4) 17(3)  -24(3) 
________________________________________________________________________ 
  
! 138!
 
Crystallographic Table 5.  Crystal data and structure refinement for (Th2), 
Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O. 
 
Identification code Th2 
Empirical formula C
12
H
32
N
12
O
17
Pt
3
Th
2
 
Formula weight 1665.85 
Temperature 295(2) K 
Wavelength  0.71073 ? 
Crystal system Monoclinic 
Space group  C2/c 
Unit cel dimensions a = 16.4915(4) ? ? = 90?. 
 b = 12.1941(4) ? ? = 114.016(4)?. 
 c = 19.5380(5) ? ? = 90?. 
Volume 3588.9(2) ?
3
 
Z 4 
Density (calculated) 3.083 Mg/m
3
 
Absorption coeficient 19.989 mm
-1
 
F(000) 2952 
Crystal size 0.29 x 0.03 x 0.03 mm
3
 
Theta range for data collection 3.34 to 30.61?. 
Index ranges -22<=h<=23, -16<=k<=17, -27<=l<=27 
Reflections collected 32269 
Independent reflections 5166 [R(int) = 0.0281] 
Completenes to theta = 29.00? 99.6 %  
Absorption correction Semi-empirical from equivalents 
Max. and min. transmision 1.0 and 0.30 
Refinement method Full-matrix least-squares on F
2
 
Data / restraints / parameters 5166 / 0 / 211 
Goodnes-of-fit on F
2
 0.918 
Final R indices [I>2sigma(I)] R1 = 0.0141, wR2 = 0.0239 
R indices (al data) R1 = 0.0211, wR2 = 0.0244 
Extinction coeficient 0.000167(4) 
Largest dif. peak and hole 0.652 and -0.703 e.?
-3 
 
 
 
 
 
 
 
 
 
! 139!
Crystallographic Table 6.  Atomic coordinates  ( x 10
4
) and equivalent  isotropic 
displacement parameters (?
2
x 10
3
) for Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O.  U(eq) is 
defined as one third of  the trace of the orthogonalized U
ij
 tensor. 
________________________________________________________________________ 
 x y z U(eq) 
________________________________________________________________________ 
Th(1) 1439(1) 1950(1) 149(1) 15(1) 
Pt(1) -838(1) 2711(1) 1667(1) 19(1) 
Pt(2) 2500 -2500 0 19(1) 
O(1) 2912(1) 1674(1) 321(1) 21(1) 
O(2) 327(1) 3347(2) -470(1) 39(1) 
O(3) 2138(1) 1128(2) 1407(1) 36(1) 
O(4) 978(1) 1541(2) -1193(1) 32(1) 
O(5) 1993(2) 3462(2) 1087(1) 41(1) 
O(6) -40(1) 1005(2) -412(1) 31(1) 
O(7) 0 2667(3) -2500 48(1) 
O(8) 1252(2) -571(2) 1772(1) 52(1) 
O(9) -1371(2) 6087(2) 2690(1) 51(1) 
C(1) -39(2) 2306(2) 1173(2) 25(1) 
C(2) -1040(2) 1152(2) 1838(2) 30(1) 
C(3) -1609(2) 3159(2) 2176(2) 28(1) 
C(4) -705(2) 4284(2) 1463(2) 30(1) 
C(5) 1985(2) -1034(2) 46(1) 22(1) 
C(6) 1855(2) -3191(2) 550(2) 32(1) 
N(1) 429(2) 2110(2) 888(1) 30(1) 
N(2) -1182(2) 261(2) 1927(2) 53(1) 
N(3) -2028(2) 3433(2) 2486(2) 47(1) 
N(4) -661(2) 5176(2) 1329(2) 49(1) 
N(5) 1694(2) -181(2) 51(1) 27(1) 
N(6) 1490(2) -3589(3) 873(2) 63(1) 
_______________________________________________________________________ 
  
! 140!
 
Crystallographic Table 7.   Bond lengths [?] and angles [?] for 
Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O. 
________________________________________________________________________     
Th(1)-O(1)  2.3369(17) 
Th(1)-O(1)#1  2.3675(17) 
Th(1)-O(2)  2.4342(18) 
Th(1)-O(3)  2.4631(18) 
Th(1)-O(4)  2.4650(18) 
Th(1)-O(5)  2.4962(19) 
Th(1)-O(6)  2.5113(18) 
Th(1)-N(1)  2.619(2) 
Th(1)-N(5)  2.651(2) 
Th(1)-Th(1)#1  4.0045(2) 
Pt(1)-C(2)  1.982(3) 
Pt(1)-C(3)  1.982(3) 
Pt(1)-C(1)  1.987(3) 
Pt(1)-C(4)  1.988(3) 
Pt(2)-C(6)#2  1.982(3) 
Pt(2)-C(6)  1.982(3) 
Pt(2)-C(5)#2  1.997(3) 
Pt(2)-C(5)  1.997(3) 
O(1)-Th(1)#1  2.3675(17) 
O(1)-H(1A)  0.8501 
O(2)-H(2A)  0.8500 
O(2)-H(2B)  0.8499 
O(3)-H(3A)  0.8500 
O(3)-H(3B)  0.8501 
O(4)-H(4A)  0.8500 
O(4)-H(4B)  0.8500 
O(5)-H(5A)  0.8500 
O(5)-H(5B)  0.8500 
O(6)-H(6A)  0.8500 
O(6)-H(6B)  0.8501 
O(7)-H(7)  0.8501 
O(8)-H(8A)  0.8499 
! 141!
O(8)-H(8B)  0.8500 
O(9)-H(9A)  0.8500 
O(9)-H(9B)  0.8500 
C(1)-N(1)  1.145(3) 
C(2)-N(2)  1.140(4) 
C(3)-N(3)  1.139(4) 
C(4)-N(4)  1.129(4) 
C(5)-N(5)  1.147(3) 
C(6)-N(6)  1.141(4) 
O(1)-Th(1)-O(1)#1 63.31(7) 
O(1)-Th(1)-O(2) 134.55(6) 
O(1)#1-Th(1)-O(2) 71.29(6) 
O(1)-Th(1)-O(3) 76.19(6) 
O(1)#1-Th(1)-O(3) 125.04(6) 
O(2)-Th(1)-O(3) 137.08(7) 
O(1)-Th(1)-O(4) 88.66(7) 
O(1)#1-Th(1)-O(4) 73.94(6) 
O(2)-Th(1)-O(4) 76.67(7) 
O(3)-Th(1)-O(4) 142.68(7) 
O(1)-Th(1)-O(5) 87.31(7) 
O(1)#1-Th(1)-O(5) 70.95(6) 
O(2)-Th(1)-O(5) 79.88(8) 
O(3)-Th(1)-O(5) 71.65(7) 
O(4)-Th(1)-O(5) 142.45(6) 
O(1)-Th(1)-O(6) 139.91(6) 
O(1)#1-Th(1)-O(6) 131.91(6) 
O(2)-Th(1)-O(6) 72.66(7) 
O(3)-Th(1)-O(6) 103.04(6) 
O(4)-Th(1)-O(6) 67.57(6) 
O(5)-Th(1)-O(6) 131.24(7) 
O(1)-Th(1)-N(1) 142.06(7) 
O(1)#1-Th(1)-N(1) 130.56(7) 
O(2)-Th(1)-N(1) 72.63(7) 
O(3)-Th(1)-N(1) 67.93(7) 
O(4)-Th(1)-N(1) 127.69(7) 
O(5)-Th(1)-N(1) 70.37(7) 
! 142!
O(6)-Th(1)-N(1) 63.37(7) 
O(1)-Th(1)-N(5) 71.54(6) 
O(1)#1-Th(1)-N(5) 123.85(7) 
O(2)-Th(1)-N(5) 139.42(7) 
O(3)-Th(1)-N(5) 69.49(7) 
O(4)-Th(1)-N(5) 73.40(6) 
O(5)-Th(1)-N(5) 139.08(7) 
O(6)-Th(1)-N(5) 70.93(7) 
N(1)-Th(1)-N(5) 105.55(7) 
O(1)-Th(1)-Th(1)#1 31.89(4) 
O(1)#1-Th(1)-Th(1)#1 31.43(4) 
O(2)-Th(1)-Th(1)#1 102.69(5) 
O(3)-Th(1)-Th(1)#1 101.54(5) 
O(4)-Th(1)-Th(1)#1 79.79(5) 
O(5)-Th(1)-Th(1)#1 77.27(5) 
O(6)-Th(1)-Th(1)#1 147.28(4) 
N(1)-Th(1)-Th(1)#1 147.64(5) 
N(5)-Th(1)-Th(1)#1 98.31(5) 
C(2)-Pt(1)-C(3) 89.65(11) 
C(2)-Pt(1)-C(1) 91.90(11) 
C(3)-Pt(1)-C(1) 178.04(11) 
C(2)-Pt(1)-C(4) 176.96(12) 
C(3)-Pt(1)-C(4) 88.88(12) 
C(1)-Pt(1)-C(4) 89.63(11) 
C(6)#2-Pt(2)-C(6) 180.00(19) 
C(6)#2-Pt(2)-C(5)#2 91.37(11) 
C(6)-Pt(2)-C(5)#2 88.63(11) 
C(6)#2-Pt(2)-C(5) 88.63(11) 
C(6)-Pt(2)-C(5) 91.37(11) 
C(5)#2-Pt(2)-C(5) 180.00(15) 
Th(1)-O(1)-Th(1)#1 116.69(7) 
Th(1)-O(1)-H(1A) 121.4 
Th(1)#1-O(1)-H(1A) 121.1 
Th(1)-O(2)-H(2A) 118.3 
Th(1)-O(2)-H(2B) 119.7 
H(2A)-O(2)-H(2B) 120.5 
! 143!
Th(1)-O(3)-H(3A) 123.6 
Th(1)-O(3)-H(3B) 120.5 
H(3A)-O(3)-H(3B) 115.6 
Th(1)-O(4)-H(4A) 124.4 
Th(1)-O(4)-H(4B) 124.7 
H(4A)-O(4)-H(4B) 110.7 
Th(1)-O(5)-H(5A) 109.8 
Th(1)-O(5)-H(5B) 128.6 
H(5A)-O(5)-H(5B) 121.4 
Th(1)-O(6)-H(6A) 129.4 
Th(1)-O(6)-H(6B) 112.5 
H(6A)-O(6)-H(6B) 112.0 
H(8A)-O(8)-H(8B) 104.9 
H(9A)-O(9)-H(9B) 108.9 
N(1)-C(1)-Pt(1) 177.6(3) 
N(2)-C(2)-Pt(1) 177.9(3) 
N(3)-C(3)-Pt(1) 177.7(3) 
N(4)-C(4)-Pt(1) 177.5(3) 
N(5)-C(5)-Pt(2) 177.6(3) 
N(6)-C(6)-Pt(2) 179.4(3) 
C(1)-N(1)-Th(1) 171.5(2) 
C(5)-N(5)-Th(1) 165.5(2) 
_____________________________________________________________  
Symmetry transformations used to generate equivalent atoms: 
#1 -x+1/2,-y+1/2,-z    #2 -x+1/2,-y-1/2,-z       
 
  
! 144!
 
Crystallographic Table 8.   Anisotropic displacement parameters  (?
2
x 10
3
) for 
Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O.  The anisotropic displacement factor exponent takes 
the form:  -2?
2
[ h
2
 a*
2
U
11
 + ...  + 2 h k a* b* U
12
 ] 
________________________________________________________________________ 
 U
11
 U
22
 U
33
 U
23
 U
13
 U
12
 
________________________________________________________________________ 
Th(1) 15(1)  15(1) 18(1)  1(1) 10(1)  1(1) 
Pt(1) 21(1)  21(1) 19(1)  1(1) 12(1)  2(1) 
Pt(2) 16(1)  16(1) 24(1)  0(1) 9(1)  2(1) 
O(1) 19(1)  17(1) 33(1)  9(1) 15(1)  5(1) 
O(2) 24(1)  38(1) 61(1)  26(1) 24(1)  11(1) 
O(3) 32(1)  48(1) 25(1)  10(1) 8(1)  -2(1) 
O(4) 44(1)  29(1) 23(1)  0(1) 13(1)  5(1) 
O(5) 61(2)  39(1) 34(1)  -15(1) 32(1)  -23(1) 
O(6) 23(1)  43(1) 29(1)  -3(1) 13(1)  -9(1) 
O(7) 61(2)  42(2) 39(2)  0 18(2)  0 
O(8) 41(1)  80(2) 32(1)  -5(1) 12(1)  9(1) 
O(9) 45(2)  66(2) 36(1)  -4(1) 11(1)  6(1) 
C(1) 23(1)  28(2) 23(1)  -1(1) 10(1)  -2(1) 
C(2) 39(2)  30(2) 27(2)  -3(1) 20(1)  4(1) 
C(3) 33(2)  27(2) 27(1)  6(1) 17(1)  6(1) 
C(4) 29(2)  34(2) 28(2)  3(1) 15(1)  1(1) 
C(5) 17(1)  23(1) 25(1)  -1(1) 7(1)  -2(1) 
C(6) 22(1)  36(2) 37(2)  7(1) 13(1)  4(1) 
N(1) 27(1)  41(2) 29(1)  -3(1) 18(1)  -1(1) 
N(2) 90(2)  28(2) 55(2)  -1(1) 42(2)  -2(2) 
N(3) 57(2)  55(2) 45(2)  11(1) 36(2)  23(2) 
N(4) 57(2)  31(2) 60(2)  14(1) 25(2)  0(1) 
N(5) 26(1)  20(1) 33(1)  -2(1) 11(1)  2(1) 
N(6) 35(2)  97(3) 64(2)  31(2) 28(2)  6(2) 
________________________________________________________________________ 
 
  
! 145!
 
Crystallographic Table 9.  Hydrogen coordinates ( x 10
4
) and isotropic displacement 
parameters (?
2
x 10 
3
) for Th
2
(H
2
O)
10
(OH)
2
[Pt(CN)
4
]
3
?5H
2
O. 
________________________________________________________________________ 
 x  y  z  U(eq) 
________________________________________________________________________ 
 
H(1A) 3224 1161 599 32 
H(2A) -179 3287 -455 58 
H(2B) 404 3789 -774 58 
H(3A) 2634 1337 1739 54 
H(3B) 1864 649 1548 54 
H(4A) 1123 964 -1361 48 
H(4B) 686 1975 -1548 48 
H(5A) 2123 4017 890 61 
H(5B) 2032 3478 1535 61 
H(6A) -392 931 -870 47 
H(6B) -316 1026 -127 47 
H(7) -404 3069 -2467 72 
H(8A) 1693 -1006 1930 78 
H(8B) 1195 -358 2164 78 
H(9A) -1049 5514 2794 76 
H(9B) -1483 6254 3064 76 
 
 
  
! 146!
 
Crystallographic Table 10  Crystal data and structure refinement for U3, 
K
3
[(UO
2
)
2
(OH)(Pt(CN)
4
)
2
]
2
?NO
3
?1.5H
2
O. 
 
Identification code                       U3 
Empirical formula                 C
16
 H
5
 K
3
 N
17
 O
14.50
 Pt
4
 U
4
 
Formula weight                     2517.15    
Temperature                        290(2) K 
Wavelength                         0.71073 ? 
Crystal system, space group        Tetragonal,  P 4/m b m 
Unit cel dimensions               a = 22.1073(2) ?    ? = 90 ?.  
                                                      b = 22.1073(2) ?    ? = 90 ?.  
                                                      c = 12.6202(2) ?    ? = 90 ?.  
Volume                                    6167.90(13) ? 
3
 
 Z, Calculated density              4,  2.711 Mg/m
3
 
 Absorption coeficient             19.750 mm
-1
 
 F(000)                             4292  
 Crystal size                       0.344 x 0.174 x 0.096 mm 
Theta range for data collection   2.91 to 26.37 ?.  
 Limiting indices                   -27<=h<=27, -25<=k<=26, -15<=l<=15  
 Reflections collected / unique     6733 / 3423 [R(int) = 0.0564]      
Completenes to theta = 26.37      99.7 %       
Absorption correction              Semi-empirical from equivalents       
Max. and min. transmision         1.00 and 0.31193       
Refinement method                  Full-matrix least-squares on F
2
       
Data / restraints / parameters     3423 / 55 / 146        
Goodnes-of-fit on F
2
             1.058  
Final R indices [I>2sigma(I)]      R1 = 0.0522, wR2 = 0.1500        
R indices (al data)               R1 = 0.0687, wR2 = 0.1562 
Largest dif. peak and hole        4.241 and -9.542 e. ? 
-3
 
 
  
! 147!
 
Crystallographic Table 11.  Atomic coordinates  ( x 10
4
) and equivalent  isotropic 
displacement parameters (?
 2
x 10
3
) for K
3
[(UO
2
)
2
(OH)(Pt(CN)
4
)
2
]
2
?NO
3
?1.5H
2
O.  
U(eq) is defined as one third of  the trace of the orthogonalized U
ij
 tensor. 
 
         ________________________________________________________________  
   
                         x             y             z           U(eq)  
         ________________________________________________________________  
   
          K(1)          607(3)       5607(3)          0          51(2)  
          K(2)         3617(7)       3695(7)      -5000         152  
          U(1)         2379(1)       5072(1)      -1713(1)       19(1)  
          Pt(1)        1464(1)       6464(1)      -5000          22(1)  
          Pt(2)        1234(1)       3766(1)      -5000          22(1)  
          Pt(3)        2432(1)       2568(1)      -1276(1)       15(1)  
          C(1)         1902(7)       6004(6)      -3904(11)      22(3)  
          C(2)         1676(8)       4216(7)      -3896(12)      26(3)  
          C(3)         2423(7)       3463(7)      -1306(12)      24(3)  
          C(4)         3325(6)       2575(7)      -1294(11)      20(3)  
          N(1)         2118(7)       5718(6)      -3255(11)      39(3)  
          N(2)         1937(7)       4471(7)      -3235(11)      39(3)  
          N(3)         2409(7)       3985(6)      -1344(11)      39(3)  
          N(4)         2579(7)       6157(6)      -1344(11)      38(3)  
          N(5)            0                5000         -2660(20)      74(11)  
          O(1)         1634(5)       5159(5)      -1214(9)       36(2)  
          O(2)         3103(5)       5001(5)      -2198(9)       33(2)  
          O(3)         2746(8)       5044(7)          0                29(3)  
          O(4)            0                5000         -1682(19)      55(5)  
          O(5)          326(12)      5326(12)     -3270(30)     210(20)  
          O(6)          728(10)      4272(10)         0               63(6)  
          O(7)            0             0          5000          56(12)  
  
! 148!
          
Crystallographic Table 12.   Bond lengths [?] and angles [?] for  
K
3
[(UO
2
)
2
(OH)(Pt(CN)
4
)
2
]
2
?NO
3
?1.5H
2
O. 
_____________________________________________________  
            K(1)-O(4)                      2.848(19)  
            K(1)-O(4)#1                  2.848(19)  
            K(1)-O(1)#2                  2.912(12)  
            K(1)-O(1)#3                  2.912(12)  
            K(1)-O(1)                     2.912(12)  
            K(1)-O(1)#4                  2.912(12)  
            K(1)-O(6)#1                  2.96(3)  
            K(1)-O(6)                      2.96(3)  
            K(1)-K(1)#1                  3.80(2)  
            U(1)-O(2)                     1.720(12)  
            U(1)-O(1)                      1.774(12)  
            U(1)-O(3)                      2.310(6)  
            U(1)-N(3)                      2.449(14)  
            U(1)-N(1)                      2.482(13)  
            U(1)-N(4)                      2.483(14)  
            U(1)-N(2)                      2.531(14)  
            Pt(1)-C(1)#5                  1.971(15)  
            Pt(1)-C(1)#4                  1.971(15)  
            Pt(1)-C(1)                      1.971(15)  
            Pt(1)-C(1)#6                  1.971(15)  
            Pt(2)-C(2)#7                  1.971(15)  
            Pt(2)-C(2)                      1.971(15)  
            Pt(2)-C(2)#8                  1.971(15)  
            Pt(2)-C(2)#6                  1.971(15)  
            Pt(3)-C(4)                      1.975(14)  
            Pt(3)-C(4)#8                  1.975(14)  
            Pt(3)-C(3)                     1.978(15)  
            Pt(3)-C(3)#8                 1.978(15)  
            Pt(3)-Pt(3)#2                3.2214(15)  
            C(1)-N(1)                     1.139(19)  
            C(2)-N(2)                     1.16(2)  
            C(3)-N(3)                      1.16(2)  
! 149!
            C(4)-N(4)#9                   1.15(2)  
            N(4)-C(4)#10                 1.15(2)  
            N(5)-O(4)                       1.238(18)  
            N(5)-O(5)#11                 1.279(18)  
            N(5)-O(5)                        1.279(18)  
            O(3)-U(1)#2                   2.310(6)  
            O(4)-K(1)#1                    2.848(19)  
            O(6)-K(1)#1                   2.96(3) 
 
            O(4)-K(1)-O(4)#1          96.4(7)  
            O(4)-K(1)-O(1)#2          126.8(3)  
            O(4)#1-K(1)-O(1)#2       79.3(3)  
            O(4)-K(1)-O(1)#3           126.8(3)  
            O(4)#1-K(1)-O(1)#3       79.3(3)  
            O(1)#2-K(1)-O(1)#3       104.7(5)  
            O(4)-K(1)-O(1)               79.3(3)  
            O(4)#1-K(1)-O(1)           126.8(3)  
            O(1)#2-K(1)-O(1)           63.5(5)  
            O(1)#3-K(1)-O(1)           143.8(6)  
            O(4)-K(1)-O(1)#4           79.3(3)  
            O(4)#1-K(1)-O(1)#4       126.8(3)  
            O(1)#2-K(1)-O(1)#4       143.8(6)  
            O(1)#3-K(1)-O(1)#4       63.5(5)  
            O(1)-K(1)-O(1)#4           104.7(5)  
            O(4)-K(1)-O(6)#1           64.7(3)  
            O(4)#1-K(1)-O(6)#1        64.7(3)  
            O(1)#2-K(1)-O(6)#1         143.8(3)  
            O(1)#3-K(1)-O(6)#1           65.9(4)  
            O(1)-K(1)-O(6)#1             143.8(3)  
            O(1)#4-K(1)-O(6)#1          65.9(4)  
            O(4)-K(1)-O(6)                64.7(3)  
            O(4)#1-K(1)-O(6)              64.7(3)  
            O(1)#2-K(1)-O(6)              65.9(4)  
            O(1)#3-K(1)-O(6)             143.8(3)  
            O(1)-K(1)-O(6)                65.9(4)  
            O(1)#4-K(1)-O(6)             143.8(3)  
! 150!
            O(6)#1-K(1)-O(6)             100.3(9)  
            O(4)-K(1)-K(1)#1              48.2(4)  
            O(4)#1-K(1)-K(1)#1         48.2(4)  
            O(1)#2-K(1)-K(1)#1        108.1(3)  
            O(1)#3-K(1)-K(1)#1        108.1(3)  
            O(1)-K(1)-K(1)#1            108.1(3)  
            O(1)#4-K(1)-K(1)#1          108.1(3)  
            O(6)#1-K(1)-K(1)#1           50.1(4)  
            O(6)-K(1)-K(1)#1              50.1(4)  
            O(2)-U(1)-O(1)             179.1(5)  
            O(2)-U(1)-O(3)              90.2(5)  
            O(1)-U(1)-O(3)              89.8(5)  
            O(2)-U(1)-N(3)              87.3(5)  
            O(1)-U(1)-N(3)                93.7(5)  
            O(3)-U(1)-N(3)             77.6(5)  
            O(2)-U(1)-N(1)            89.4(5)  
            O(1)-U(1)-N(1)            90.0(5)  
            O(3)-U(1)-N(1)            146.2(5)  
            N(3)-U(1)-N(1)             136.1(5)  
            O(2)-U(1)-N(4)                89.4(5)  
            O(1)-U(1)-N(4)                89.7(5)  
            O(3)-U(1)-N(4)                77.8(5)  
            N(3)-U(1)-N(4)               155.1(5)  
            N(1)-U(1)-N(4)                68.5(5)  
            O(2)-U(1)-N(2)                92.3(5)  
            O(1)-U(1)-N(2)                88.2(5)  
            O(3)-U(1)-N(2)               146.2(5)  
            N(3)-U(1)-N(2)                68.9(5)  
            N(1)-U(1)-N(2)                67.5(5)  
            N(4)-U(1)-N(2)                135.9(5)  
            C(1)#5-Pt(1)-C(1)#4           89.1(8)  
            C(1)#5-Pt(1)-C(1)            178.0(9)  
            C(1)#4-Pt(1)-C(1)             90.8(8)  
            C(1)#5-Pt(1)-C(1)#6          90.8(8)  
            C(1)#4-Pt(1)-C(1)#6         178.0(9)  
            C(1)-Pt(1)-C(1)#6             89.1(8)  
! 151!
            C(2)#7-Pt(2)-C(2)            179.3(10)  
            C(2)#7-Pt(2)-C(2)#8           90.0(8)  
            C(2)-Pt(2)-C(2)#8             90.0(8)  
            C(2)#7-Pt(2)-C(2)#6           90.0(8)  
            C(2)-Pt(2)-C(2)#6             90.0(8)  
            C(2)#8-Pt(2)-C(2)#6         179.3(10)  
            C(4)-Pt(3)-C(4)#8             90.8(9)  
            C(4)-Pt(3)-C(3)               90.1(6)  
            C(4)#8-Pt(3)-C(3)            178.0(6)  
            C(4)-Pt(3)-C(3)#8            178.0(6)  
            C(4)#8-Pt(3)-C(3)#8           90.1(6)  
            C(3)-Pt(3)-C(3)#8             88.9(9)  
            C(4)-Pt(3)-Pt(3)#2            90.6(4)  
            C(4)#8-Pt(3)-Pt(3)#2         90.6(4)  
            C(3)-Pt(3)-Pt(3)#2            91.1(4)  
            C(3)#8-Pt(3)-Pt(3)#2          91.1(4)  
            N(1)-C(1)-Pt(1)              175.3(15)  
            N(2)-C(2)-Pt(2)              178.8(15)  
            N(3)-C(3)-Pt(3)              178.3(15)  
            N(4)#9-C(4)-Pt(3)            177.5(13)  
            C(1)-N(1)-U(1)               168.5(15)  
            C(2)-N(2)-U(1)               172.8(15)  
            C(3)-N(3)-U(1)               171.4(13)  
            C(4)#10-N(4)-U(1)           166.7(13)  
            O(4)-N(5)-O(5)#11           127(2) 
            O(4)-N(5)-O(5)               127(2)  
            O(5)#11-N(5)-O(5)           106(5)  
            U(1)-O(1)-K(1)               161.3(6)  
            U(1)-O(3)-U(1)#2            138.7(8)  
            N(5)-O(4)-K(1)               138.2(4)  
            N(5)-O(4)-K(1)#1            138.2(4)  
            K(1)-O(4)-K(1)#1             83.6(7)  
            K(1)-O(6)-K(1)#1             79.7(9)  
 _____________________________________________________________  
Symmetry transformations used to generate equivalent atoms: 
           #1 -x,-y+1,-z    #2 x,y,-z    #3 y-1/2,x+1/2,-z      
! 152!
           #4 y-1/2,x+1/2,z    #5 y-1/2,x+1/2,-z-1      
           #6 x,y,-z-1    #7 -y+1/2,-x+1/2,-z-1      
           #8 -y+1/2,-x+1/2,z    #9 -y+1,x,z    #10 y,-x+1,z      
           #11 -x,-y+1,z      
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
! 153!
 
Crystallographic Table 13.   Anisotropic displacement parameters  (?
 2
x 10
3
) for 
K
3
[(UO
2
)
2
(OH)(Pt(CN)
4
)
2
]
2
?NO
3
?1.5H
2
O.  The anisotropic displacement factor 
exponent takes the form:  -2?
2
[ h
2
 a*
2
U
11
 + ...  + 2 h k a* b* U
12
 ] 
________________________________________________________________________ 
 U
11
        U
22
   U
33  
U
23 
U
13
 U
12
 
_______________________________________________________________________ 
K(1)        50(3)      50(3)          53(5)              0                 0             5(4)  
U(1)        27(1)      11(1)          18(1)              0(1)           -2(1)       -1(1)  
Pt(1)        25(1)      25(1)          14(1)              0                 0            5(1)  
Pt(2)        25(1)      25(1)          15(1)              0                 0           -8(1)  
Pt(3)        11(1)      11(1)          23(1)              0(1)            0(1)        0(1)  
C(1)         36(9)      13(7)         17(6)             -5(5)             0(6)      -1(6)  
C(2)         36(9)      22(8)         21(7)              4(6)             2(6)     -12(7)  
C(3)         24(8)      16(5)         33(8)             -8(6)             1(7)       2(6)  
C(4)          9(6)       27(8)         24(7)              4(6)            -5(5)      -1(5)  
N(1)        55(10)     29(7)         33(6)              9(5)          -12(6)       0(7)  
N(2)        53(9)       32(7)         30(6)             -2(5)          -11(6)    -13(7)  
N(3)        58(10)     20(4)         39(7)              2(5)          -10(7)       2(5)  
N(4)        55(10)     22(5)         36(7)              2(5)           -8(7)      -8(6)  
N(5)        86(17)     86(17)       48(10)            0                0            20(20)  
O(1)        31(5)       37(6)         41(6)            -4(5)            1(4)         0(4)  
O(2)        34(5)       31(6)         35(5)             1(5)            1(4)         0(4)  
O(3)        36(8)       29(8)         22(5)             0                0            -3(7)  
O(4)        61(8)       61(8)        45(10)            0                 0            -8(12)  
O(5)      240(30)    240(30)    140(30)       100(20)      100(20)     20(40)  
O(6)        54(8)       54(8)        83(18)            0                 0          -16(10)  
O(7)        72(19)     72(19)      22(17)            0                 0              0  
 
________________________________________________________________________ 
  
! 154!
 
 
 
Crystallographic Table 14.  Crystal data and structure refinement for 
{U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O (U4) .  
   
   
Identification code U4    
Empirical formula C
12
 N
12
 O
15
 Pt
3
 U
2
 
Formula weight 1613.57   
Temperature 183(2) K   
Wavelength 0.71073 ? 
Crystal system, space group Triclinic,  P-1   
Unit cel dimensions a = 9.716(4) ?    ? = 74.191(7) ? 
 b = 9.823(4) ?    ? = 70.734(7) ? 
 c = 9.926(4) ?    ? = 67.242(7) ? 
Volume 813.2(6) ?
 3
 
Z, Calculated density  1,  3.295 Mg/m
3
 
Absorption coeficient 22.857 mm
-1
 
F(000)  694  
Crystal size 0.10 x 0.10 x 0.10 mm 
Theta range for data collection 2.28 to 28.31 deg.  
Limiting indices -12<=h<=12, -13<=k<=13, -13<=l<=13  
Reflections collected / unique 7998 / 3940  
[R(int) = 0.0582]  
Completenes to theta = 28.31   97.7 %  
Absorption correction Numerical 
Max. and min. transmision 0.2083 and 0.2083  
Refinement method Full-matrix least-squares on F
2
 
Data / restraints / parameters 3940 / 0 / 184  
Goodnes-of-fit on F
2
 1.103  
Final R indices [I>2sigma(I)] R1 = 0.0669, wR2 = 0.1618  
R indices (al data)  R1 = 0.0781, wR2 = 0.1681  
Largest dif. peak and hole 3.760 and -4.888 e. ?
-3
 
! 155!
 
Crystallographic Table 15.  Atomic coordinates ( x 10
4
) and equivalent isotropic 
displacement parameters (?
2
 x 10
3
) for {U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O. U(eq) is 
defined as one third of the trace of the orthogonalized Uij tensor.  
   
         ________________________________________________________________  
   
                               x                    y                  z             U(eq)  
         ________________________________________________________________  
   
          U(1)           3933(1)      -6003(1)       4254(1)       18(1)  
          N(1)        -3216(15)      2390(15)      3598(15)      27(3)  
          N(2)         2717(15)     -3189(14)      3459(16)      26(3)  
          N(3)         1899(12)      1804(13)      2245(13)      17(1)  
          N(4)        -2136(13)     -2455(13)      4513(13)      17(1)  
          N(5)        -1730(20)      3471(18)      9774(19)      45(4)  
          N(6)        -3250(20)      -370(20)     11280(20)      58(5)  
          Pt(1)        -140(1)           -286(1)         3396(1)       17(1)  
          Pt(2)           0                      0              10000          24(1)  
         C(1)        -2092(16)      1456(14)      3509(16)      18(3)  
          C(2)         1741(18)     -2101(16)      3400(18)      24(3)  
          C(3)         1085(15)      1104(15)      2659(16)      17(1)  
          C(4)        -1371(17)     -1665(16)      4100(18)      26(3)  
          C(5)        -1080(20)      2204(19)      9828(19)      38(5)  
          C(6)        -2063(19)      -330(20)     10779(19)      32(4)  
          O(1)         5000                -5000            5000          28(4)  
          O(2)         5195(14)     -5176(13)      1741(13)      36(3)  
          O(3)         4603(16)     -7770(15)      6431(14)      40(3)  
          O(4)         4464(16)     -8043(18)      2930(19)      55(4)  
          O(5)         1764(15)     -4828(15)      6247(16)      45(3)  
          O(6)         1874(16)     -5401(15)      2975(17)      45(3)  
          O(7)         5120(20)     -2350(20)       600(20)      85(6)  
          O(8)         1570(30)     -5930(20)      9090(20)      89(7)          
________________________________________________________________  
 
! 156!
 
 Crystallographic Table 16.  Bond lengths [?] and angles [?] for 
{U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O.  
           _____________________________________________________________  
   
            U(1)-O(1)                       2.0706(7)  
            U(1)-O(2)                       2.456(12)  
            U(1)-O(3)                       2.473(12)  
            U(1)-O(4)                       2.489(13)  
            U(1)-O(5)                       2.509(12)  
            U(1)-O(6)                       2.514(13)  
            U(1)-N(4)#1                   2.543(12)  
            U(1)-N(2)                       2.561(13)  
            U(1)-N(1)#2                   2.565(13)  
            N(1)-C(1)                       1.117(18)  
            N(1)-U(1)#3                   2.565(13)  
            N(2)-C(2)                       1.125(19)  
            N(3)-C(3)                       1.148(19)  
            N(4)-C(4)                       1.18(2)  
            N(4)-U(1)#1                   2.543(12)  
            N(5)-C(5)                       1.15(2)  
            N(6)-C(6)                       1.11(2)  
            Pt(1)-C(4)                      1.985(18)  
            Pt(1)-C(3)                      1.989(14)  
            Pt(1)-C(1)                      1.997(13)  
            Pt(1)-C(2)                      2.000(15)  
            Pt(1)-Pt(2)                     6.685(3)  
            Pt(2)-C(5)#4                  1.995(17)  
            Pt(2)-C(5)                      1.995(17)  
            Pt(2)-C(6)                      2.014(18)  
            Pt(2)-C(6)#4                  2.014(18)  
            O(1)-U(1)#5                   2.0706(7)  
 
            O(1)-U(1)-O(2)              90.5(3)  
            O(1)-U(1)-O(3)              75.9(3)  
            O(2)-U(1)-O(3)              139.6(4)  
            O(1)-U(1)-O(4)              142.7(3)  
            O(2)-U(1)-O(4)              74.7(5)  
            O(3)-U(1)-O(4)              93.3(6)  
            O(1)-U(1)-O(5)              78.9(3)  
            O(2)-U(1)-O(5)              137.0(4)  
            O(3)-U(1)-O(5)              78.2(5)  
            O(4)-U(1)-O(5)              134.5(5)  
            O(1)-U(1)-O(6)              142.0(3)  
            O(2)-U(1)-O(6)              77.9(5)  
            O(3)-U(1)-O(6)              134.2(5)  
! 157!
            O(4)-U(1)-O(6)               68.9(5)  
            O(5)-U(1)-O(6)                  85.4(5)  
            O(1)-U(1)-N(4)#1              134.0(3)  
            O(2)-U(1)-N(4)#1              135.5(4)  
            O(3)-U(1)-N(4)#1              66.8(4)  
            O(4)-U(1)-N(4)#1              67.6(4)  
            O(5)-U(1)-N(4)#1              68.1(4)  
            O(6)-U(1)-N(4)#1              67.4(4)  
            O(1)-U(1)-N(2)                  75.1(3)  
            O(2)-U(1)-N(2)                  68.5(4)  
            O(3)-U(1)-N(2)                  139.2(5)  
            O(4)-U(1)-N(2)                  126.8(5)  
            O(5)-U(1)-N(2)                  68.5(5)  
            O(6)-U(1)-N(2)                  66.9(4)  
            N(4)#1-U(1)-N(2)              117.8(4)  
            O(1)-U(1)-N(1)#2              76.7(3)  
            O(2)-U(1)-N(1)#2              69.1(4)  
            O(3)-U(1)-N(1)#2              70.7(5)  
            O(4)-U(1)-N(1)#2              66.0(5)  
            O(5)-U(1)-N(1)#2              144.2(5)  
            O(6)-U(1)-N(1)#2              129.3(5)  
            N(4)#1-U(1)-N(1)#2          113.2(4)  
            N(2)-U(1)-N(1)#2              128.1(5)  
            C(1)-N(1)-U(1)#3              164.9(13)  
            C(2)-N(2)-U(1)                  155.2(13)  
            C(4)-N(4)-U(1)#1              171.5(12)  
            C(4)-Pt(1)-C(3)                  179.1(6)  
            C(4)-Pt(1)-C(1)                  89.5(6)  
            C(3)-Pt(1)-C(1)                  90.2(6)  
            C(4)-Pt(1)-C(2)                  87.4(6)  
            C(3)-Pt(1)-C(2)                  92.9(6)  
            C(1)-Pt(1)-C(2)                 176.2(6)  
            C(4)-Pt(1)-Pt(2)                 94.7(5)  
            C(3)-Pt(1)-Pt(2)                 86.2(4)  
            C(1)-Pt(1)-Pt(2)                 90.8(4)  
            C(2)-Pt(1)-Pt(2)                 87.2(5)  
            C(5)#4-Pt(2)-C(5)              180.000(3)  
            C(5)#4-Pt(2)-C(6)              90.7(8)  
            C(5)-Pt(2)-C(6)                  89.3(8)  
            C(5)#4-Pt(2)-C(6)#4          89.3(8)  
            C(5)-Pt(2)-C(6)#4              90.7(8)  
            C(6)-Pt(2)-C(6)#4              180.0(4)  
            C(5)#4-Pt(2)-Pt(1)             86.0(5)  
            C(5)-Pt(2)-Pt(1)                 94.0(5)  
            C(6)-Pt(2)-Pt(1)                 88.5(5)  
            C(6)#4-Pt(2)-Pt(1)             91.5(5)  
! 158!
            N(1)-C(1)-Pt(1)                 177.2(14)  
            N(2)-C(2)-Pt(1)                174.2(14)  
            N(3)-C(3)-Pt(1)                174.3(11)  
            N(4)-C(4)-Pt(1)                178.3(12)  
            N(5)-C(5)-Pt(2)                177.9(17)  
            N(6)-C(6)-Pt(2)                172.0(19)  
            U(1)-O(1)-U(1)#5            180.000(18)            
_____________________________________________________________  
   
           Symmetry transformations used to generate equivalent atoms: 
           #1 -x,-y,-z+2    #2 x-1,y+1,z    #3 -x,-y-1,-z+1      
           #4 x+1,y-1,z    #5 -x+1,-y-1,-z+1      
 
! 159!
 
 Crystallographic Table 17.  Anisotropic displacement parameters (?
2
 x 10
3
) for       
{U
2
(H
2
O)
10
(O)[Pt(CN)
4
]
3
}?4H
2
O.  The anisotropic displacement factor exponent takes 
the form: -2 ?^2 [ h^2 a*^2 U11 + ... + 2 h k a* b* U12 ]. 
   
    
_______________________________________________________________________  
   
                  U11       U22        U33        U23         U13         U12  
    
_______________________________________________________________________  
 
    U(1)     12(1)       14(1)       28(1)       -7(1)       -3(1)      -2(1)  
    N(1)     27(7)       20(6)       32(7)      -14(5)      -7(6)       2(5)  
    N(2)     22(6)       19(6)       37(8)      -4(6)     - 10(6)      -6(5)  
    N(3)     11(1)       14(1)       25(1)      -6(1)        -3(1)      -1(1)  
    N(4)     11(1)       14(1)       25(1)      -6(1)        -3(1)      -1(1)  
    N(5)     53(10)      29(8)      42(10)    -7(7)        -10(8)      -2(8)  
    N(6)     38(10)      66(13)    55(12)     3(10)       0(9)     -21(9)  
    Pt(1)    11(1)       14(1)        25(1)      -6(1)        -3(1)      -1(1)  
    Pt(2)    22(1)       23(1)        22(1)      -6(1)        -2(1)      -4(1)  
    C(1)     20(7)       11(6)        22(7)      -2(5)        -6(6)      -4(5)  
    C(2)     24(7)        20(7)       30(9)      -9(6)        -3(7)      -9(6)  
    C(3)     11(1)       14(1)        25(1)      -6(1)        -3(1)      -1(1)  
    C(4)     18(7)       18(7)        32(9)      -6(6)        -13(7)       9(6)  
    C(5)     44(10)      25(8)       30(9)      -8(7)        -9(8)       6(8)  
    C(6)     24(8)       36(9)        28(9)      -4(7)        -1(7)      -7(7)  
    O(1)     17(7)       11(6)        49(11)    -4(7)        -8(7)       2(6) 
    O(2)     36(7)       29(6)        32(7)      -3(5)        -2(6)      -4(5)  
    O(3)     46(8)       48(8)        37(8)      14(6)       -21(6)     -32(7)  
    O(4)     33(7)       63(9)        80(11)    -53(9)       5(7)     -16(7)  
    O(5)     36(7)       39(7)        50(9)      -17(6)       9(6)     -12(6)  
    O(6)     43(8)       36(7)        66(10)     1(7)         -34(7)     -14(6)  
    O(7)     72(13)     86(14)      102(16)   29(12)    -40(12)    -44(11)  
    O(8)    125(18)    83(14)       61(12)    -33(11)    -3(12)    -41(13)     
_______________________________________________________________________  
 
 
  
! 160!
Crystallographic Table 18.  Crystal data and structure refinement for      
{Th
2
(H
2
O)
10
(OH)
2
[Pd(CN)
4
]
3
?
.
8H
2
O, Th5.  
   
   
  Identification code Th5 
  Empirical formula C
12
 N
12
 O
20
 Pd
3
 Th
2
 
  Formula weight 1415.52  
  Temperature 183(2) K 
  Wavelength  0.71073 ? 
  Crystal system, space group Triclinic,  P-1  
  Unit cel dimensions a = 9.6141(6) ?    ? = 73.7480(10) ? 
 b = 9.9479(6) ?    ? = 78.0950(10) ? 
 c= 11.1360(7) ?    ? = 68.6530(10) ? 
  Volume 945.82(10) ? 
3
 
  Z, Calculated density     1,  2.485 Mg/m
3
 
  Absorption coeficient 9.315 mm
1
 
  F(000) 634  
  Crystal size 0.10 x 0.10 x 0.10 mm 
  Theta range for data collection  1.92 to 28.30 deg.  
   Limiting indices -12<=h<=11, -13<=k<=13, -14<=l<=14  
   Reflections collected / unique 9619 / 4604 [R(int) = 0.0270]  
   Completenes to theta = 28.30  98.0 %  
   Absorption correction None 
   Max. and min. transmision  0.4560 and 0.4560  
   Refinement method  Full-matrix least-squares on F
2
 
   Data / restraints / parameters 4604 / 0 / 223  
   Goodnes-of-fit on F
2
 1.055  
   Final R indices [I>2sigma(I)]  R1 = 0.0282, wR2 = 0.0705    
   R indices (al data) R1 = 0.0307, wR2 = 0.0715  
   Largest dif. peak and hole 1.971 and -1.153 e. ?
-3
 
 
! 161!
 
         Crystallographic Table 19.  Atomic coordinates ( x 10
4
) and equivalent isotropic 
         displacement parameters (?
 2
 x 10
3
) for {Th
2
(H
2
O)
10
(OH)
2
[Pd(CN)
4
]
3
}?8H
2
O.  
         U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.  
   
         ________________________________________________________________  
   
                                x                  y                  z           U(eq)  
         ________________________________________________________________  
   
          Th(1)  14489(1)       4502(1)       3568(1)        14(1) 
          Pd(1)       10269(1)       6655(1)        -29(1)          15(1) 
          Pd(2)         10000         10000              0               19(1)  
          C(1)        11742(6)       5874(5)       1220(5)         19(1)  
          C(2)        11950(6)       6406(6)      -1433(5)        19(1)  
          C(3)         8729(6)       7455(6)      -1214(5)         22(1)  
          C(4)         8649(6)       6816(5)       1402(5)          20(1)  
          C(5)        12223(6)       9136(6)       -235(5)          23(1)  
          C(6)        10053(6)       9469(6)       1838(5)         25(1)  
          N(1)        12559(5)       5457(5)       1968(5)         26(1)  
          N(2)        12946(5)       6228(5)      -2209(5)        23(1)  
          N(3)         7840(6)       7917(6)      -1900(5)         35(1)  
          N(4)         7757(6)       6832(6)       2270(5)          32(1)  
          N(5)        13498(6)       8561(6)       -337(5)          32(1)  
          N(6)        10063(6)       9136(6)       2920(5)         35(1)  
          O(1)        15863(4)       5615(4)       4239(3)         15(1)  
          O(2)        14684(4)       2638(4)       2358(4)         24(1)  
          O(3)        12531(4)       3314(4)       4517(4)         25(1)  
          O(4)        15960(5)       1979(4)       4598(4)         30(1)  
          O(6)        12295(4)       6616(4)       4095(4)         29(1)  
          O(7)        14774(5)       6731(4)       1867(4)         33(1)  
          O(8)         6790(5)       9365(4)       3782(4)          30(1)  
          O(9)        10241(5)       6175(5)       6143(4)         35(1)  
          O(10)        4255(7)       9248(5)       2909(5)         51(1)  
          O(11)      9840(50)      9160(20)      5551(16)     460(20)          
________________________________________________________________  
 
! 162!
 
 Crystallographic Table 20.  Bond lengths [?] and angles [?] for 
{Th
2
(H
2
O)
10
(OH)
2
[Pd(CN)
4
]
3
}?8H
2
O.  
           _____________________________________________________________  
   
            Th(1)-O(1)                     2.337(3)  
            Th(1)-O(1)#1                   2.371(3)  
            Th(1)-O(4)                     2.468(4)  
            Th(1)-O(3)                     2.482(4)  
            Th(1)-O(6)                     2.484(4)  
            Th(1)-O(2)                     2.516(3) 
            Th(1)-O(7)                     2.541(4)  
            Th(1)-N(1)                     2.579(5)  
            Th(1)-N(2)#2                   2.582(5)  
            Th(1)-Th(1)#1                  3.9858(4)  
            Pd(1)-C(3)                     1.981(5)  
            Pd(1)-C(4)                     1.982(5)  
            Pd(1)-C(1)                     1.988(5)  
            Pd(1)-C(2)                     2.000(5)  
            Pd(1)-Pd(2)                    3.2511(4)  
            Pd(2)-C(6)                     1.973(6)  
            Pd(2)-C(6)#3                   1.973(6)  
            Pd(2)-C(5)                     1.983(6)  
            Pd(2)-C(5)#3                   1.983(6)  
            Pd(2)-Pd(1)#3                  3.2511(4)  
            C(1)-N(1)                      1.150(7)  
            C(2)-N(2)                      1.147(7)  
            C(3)-N(3)                      1.146(7)  
            C(4)-N(4)                      1.152(7)  
            C(5)-N(5)                      1.145(7)  
            C(6)-N(6)                      1.157(8)  
            N(2)-Th(1)#2                   2.582(4)  
            O(1)-Th(1)#1                   2.371(3)  
 
   
 
            O(1)-Th(1)-O(1)#1             64.30(13)  
            O(1)-Th(1)-O(4)               93.27(13)  
            O(1)#1-Th(1)-O(4)             72.64(13)  
            O(1)-Th(1)-O(3)              137.15(12)  
            O(1)#1-Th(1)-O(3)             73.01(12)  
            O(4)-Th(1)-O(3)               77.08(14)  
            O(1)-Th(1)-O(6)               84.07(13)  
            O(1)#1-Th(1)-O(6)             69.66(12)  
            O(4)-Th(1)-O(6)              139.25(14)  
 
! 163!
            O(3)-Th(1)-O(6)               77.70(13)  
            O(1)-Th(1)-O(2)              144.27(12)  
            O(1)#1-Th(1)-O(2)            131.48(12)  
            O(4)-Th(1)-O(2)               68.76(13)  
            O(3)-Th(1)-O(2)               70.67(13)  
            O(6)-Th(1)-O(2)              129.88(13)  
            O(1)-Th(1)-O(7)               70.53(12)  
            O(1)#1-Th(1)-O(7)            124.53(12)  
            O(4)-Th(1)-O(7)              141.48(15)  
            O(3)-Th(1)-O(7)              138.16(13)  
            O(6)-Th(1)-O(7)               75.43(14)  
            O(2)-Th(1)-O(7)              103.99(14)  
            O(1)-Th(1)-N(1)              133.45(13)  
            O(1)#1-Th(1)-N(1)            130.54(14)  
            O(4)-Th(1)-N(1)              132.15(14)  
            O(3)-Th(1)-N(1)               73.74(14)  
            O(6)-Th(1)-N(1)               68.24(14)  
            O(2)-Th(1)-N(1)               66.17(13)  
            O(7)-Th(1)-N(1)               66.76(14)  
            O(1)-Th(1)-N(2)#2             77.45(13)  
            O(1)#1-Th(1)-N(2)#2          125.54(13)  
            O(4)-Th(1)-N(2)#2             72.47(15) 
            O(3)-Th(1)-N(2)#2            135.05(14)  
            O(6)-Th(1)-N(2)#2            144.56(14)  
            O(2)-Th(1)-N(2)#2             67.87(13)  
            O(7)-Th(1)-N(2)#2             70.00(15)  
            N(1)-Th(1)-N(2)#2            103.85(15)  
            O(1)-Th(1)-Th(1)#1            32.41(8)  
            O(1)#1-Th(1)-Th(1)#1          31.90(8)  
            O(4)-Th(1)-Th(1)#1            81.72(10)  
            O(3)-Th(1)-Th(1)#1           104.84(9)  
            O(6)-Th(1)-Th(1)#1            74.50(10)  
            O(2)-Th(1)-Th(1)#1           150.45(9)  
            O(7)-Th(1)-Th(1)#1            98.15(9)  
            N(1)-Th(1)-Th(1)#1           142.17(10)  
            N(2)#2-Th(1)-Th(1)#1         102.61(10)  
            C(3)-Pd(1)-C(4)               89.6(2)  
            C(3)-Pd(1)-C(1)              177.5(2)  
            C(4)-Pd(1)-C(1)               87.9(2)  
            C(3)-Pd(1)-C(2)               92.1(2)  
            C(4)-Pd(1)-C(2)              177.6(2)  
            C(1)-Pd(1)-C(2)               90.4(2)  
            C(3)-Pd(1)-Pd(2)              90.37(15)  
            C(4)-Pd(1)-Pd(2)              85.76(14)  
            C(1)-Pd(1)-Pd(2)              89.07(14)  
 
! 164!
            C(2)-Pd(1)-Pd(2)              95.97(14)  
            C(6)-Pd(2)-C(6)#3            180.00(9)  
            C(6)-Pd(2)-C(5)               89.3(2)  
            C(6)#3-Pd(2)-C(5)             90.7(2)  
            C(6)-Pd(2)-C(5)#3             90.7(2)  
            C(6)#3-Pd(2)-C(5)#3           89.3(2)  
            C(5)-Pd(2)-C(5)#3            180.00(16)  
            C(6)-Pd(2)-Pd(1)              91.79(16)  
            C(6)#3-Pd(2)-Pd(1)            88.21(16)  
            C(5)-Pd(2)-Pd(1)              81.32(15)  
            C(5)#3-Pd(2)-Pd(1)            98.68(15)  
            C(6)-Pd(2)-Pd(1)#3            88.21(16)  
            C(6)#3-Pd(2)-Pd(1)#3          91.79(16) 
            C(5)-Pd(2)-Pd(1)#3            98.68(15)  
            C(5)#3-Pd(2)-Pd(1)#3          81.32(15)  
            Pd(1)-Pd(2)-Pd(1)#3          180.0  
            N(1)-C(1)-Pd(1)              177.5(5)  
            N(2)-C(2)-Pd(1)              177.6(5) 
            N(3)-C(3)-Pd(1)              179.9(7)  
            N(4)-C(4)-Pd(1)              176.1(5)  
            N(5)-C(5)-Pd(2)              176.1(5)  
            N(6)-C(6)-Pd(2)              178.3(5)  
            C(1)-N(1)-Th(1)              177.5(5)  
            C(2)-N(2)-Th(1)#2            168.0(4)  
            Th(1)-O(1)-Th(1)#1           115.70(13)            
_____________________________________________________________  
   
           Symmetry transformations used to generate equivalent atoms: 
           #1 -x+3,-y+1,-z+1    #2 -x+3,-y+1,-z      
           #3 -x+2,-y+2,-z      
  
! 165!
 
 
 Crystallographic Table 21.  Anisotropic displacement parameters (A
2
 x 10
3
) for 
{Th
2
(H
2
O)
10
(OH)
2
[Pd(CN)
4
]
3
}?8H
2
O. The anisotropic displacement factor exponent 
takes the form: -2 ?
2
 [ h
2
 a*
2
 U11 + ... + 2 h k a* b* U12 ]  
   
    
_______________________________________________________________________  
   
                 U11        U22        U33        U23        U13        U12  
    
_______________________________________________________________________  
   
    Th(1)    11(1)      18(1)      11(1)      -3(1)      -1(1)      -4(1)  
    Pd(1)    11(1)      19(1)      13(1)      -4(1)      -1(1)      -4(1)  
    Pd(2)    18(1)      17(1)      19(1)      -3(1)      -3(1)      -3(1)  
    C(1)     18(2)      19(2)      19(2)      -3(2)      -3(2)      -7(2)  
    C(2)     14(2)      25(2)      19(3)      -4(2)      -3(2)      -8(2)  
    C(3)     20(3)      25(2)      24(3)      -9(2)      -2(2)      -8(2)  
    C(4)     17(2)      21(2)      23(3)      -4(2)       0(2)      -7(2)  
    C(5)     26(3)      24(2)      18(3)      -6(2)      -2(2)      -7(2)  
    C(6)     23(3)      26(2)      24(3)      -6(2)      -4(2)      -6(2)  
    N(1)     25(2)      27(2)      23(2)      -2(2)      -9(2)      -6(2)  
    N(2)     17(2)      28(2)      27(2)     -12(2)       1(2)      -8(2)  
    N(3)     34(3)      31(3)      40(3)      -7(2)     -17(3)      -5(2)  
    N(4)     32(3)      35(3)      29(3)     -11(2)      10(2)     -17(2)  
    N(5)     22(3)      36(3)      34(3)     -10(2)      -1(2)      -3(2)  
    N(6)     33(3)      39(3)      27(3)      -3(2)      -7(2)      -5(2)  
    O(1)     15(2)      22(2)      12(2)      -3(1)      -1(1)     -10(1)  
    O(2)     19(2)      28(2)      30(2)     -17(2)      -3(2)      -5(2)  
    O(3)     22(2)      29(2)      23(2)       1(2)      -4(2)     -13(2)  
    O(4)     36(2)      18(2)      26(2)      -2(2)      -9(2)       1(2)  
    O(6)     18(2)      32(2)      23(2)      -3(2)       1(2)       4(2)  
    O(7)     42(3)      32(2)      26(2)      10(2)     -19(2)     -18(2)  
    O(8)     32(2)      25(2)      28(2)      -4(2)       0(2)      -8(2)  
    O(9)     22(2)      55(3)      27(2)      -8(2)      -2(2)     -12(2)  
    O(10)    65(4)      34(2)      57(3)      -7(2)     -32(3)      -7(2)  
    O(11)  1090(80)    260(20)    119(14)    -52(15)     50(30)   -360(40)     
_______________________________________________________________________  
 
 
  
! 166!
Crystallographic Table 22  Crystal data and structure refinement for 
U6,{(UO
2
)
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]}. 
   
   
      Identification code               U6 
      Empirical formula                  C
24
 H
48
 N
8
 Ni
2
 O
20
 S
8
 U
4
 
      Formula weight                     2094.72  
      Temperature                        183(2) K 
      Wavelength                        0.71073 ? 
      Crystal system, space group       Monoclinic,  C 2/c 
      Unit cel dimensions              a = 21.5224(11) ?  ? = 90 ? 
                                                    b = 10.2531(5) ?    ? = 111.9430(10)?  
                                                      c = 13.3170(6) ?    ? = 90 ? 
      Volume                            2725.8(2) ?
 3
 
      Z, Calculated density              2,  2.552 Mg/m
3
 
      Absorption coeficient             2.892 mm
-1
 
      F(000)                           1920  
      Crystal size                       0.10 x 0.10 x 0.10 mm 
      Theta range for data collection    2.04 to 28.32 ? 
      Limiting indices                   -28<=h<=25, -13<=k<=13, -12<=l<=17  
      Reflections collected / unique     10040 / 3358 [R(int) = 0.0292]  
      Completenes to theta = 28.32     98.9 %  
      Absorption correction             Empirical 
      Max. and min. transmision         0.3588 and 0.3588  
      Refinement method                  Full-matrix least-squares on F
2
 
      Data / restraints / parameters     3358 / 0 / 146  
      Goodnes-of-fit on F
2 
1.057  
      Final R indices [I>2sigma(I)]      R1 = 0.0298, wR2 = 0.0724  
      R indices (al data)               R1 = 0.0346, wR2 = 0.0746  
      Largest dif. peak and hole        1.937 and -1.110 e. ? 
-3 
 
 
 
 
 
         
  
! 167!
Crystallographic Table 23.  Atomic coordinates ( x 10
4
) and equivalent isotropic 
displacement parameters (?
 2
 x 10
3
) for {(UO
2
)
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]}. U(eq) is 
defined as one third of the trace of the orthogonalized  Uij tensor.  
   
         ________________________________________________________________  
   
                          x              y              z           U(eq)  
         ________________________________________________________________  
   
          Ni(1) 5000 7183(1)  2500 21(1)  
          U(1) 3110(1) 11034(1) 503(1) 20(1)  
          O(1) 3164(2) 11299(4) 1851(3) 27(1)  
          O(2) 3113(2) 10683(4) -803(3) 32(1)  
          O(3)          2997(2) 13276(3) 186(4) 29(1)   
          O(5) 2493(2) 9073(3) 374(3) 27(1)  
          O(6) 4224(2) 11862(4) 1002(4) 34(1)  
          C(1) 4375(3) 8440(5) 1758(5) 26(1)  
          C(2) 4373(3) 5883(5) 1834(6) 32(1)  
          C(3) 1886(3) 9276(6) 1750(6) 39(2)  
          C(4)          2834(3) 7466(6) 2013(5)  37(1)  
          C(5) 5472(6) 11375(11)      1315(10)     86(3)  
          C(6) 4797(6)  13323(11)    17(10)      86(3)  
          S(1) 2159(1) 8211(1) 953(1)   29(1)  
          S(2) 4682(1) 11754(2)        354(1)       40(1)  
          N(1) 3979(2) 9209(4)       1294(4)       30(1)  
          N(2) 3995(3)  5090(5)  1436(6)    49(2)  
         ________________________________________________________________  
 
 
 
 
 
 
 
 
         
  
! 168!
   Crystallographic Table 24.  Bond lengths [?] and angles [?] for         
{(UO
2
)
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]}.  
           _____________________________________________________________  
   
            Ni(1)-C(1)#1                   1.858(5)  
            Ni(1)-C(1)                     1.858(5)  
            Ni(1)-C(2)                     1.868(6)  
            Ni(1)-C(2)#1                   1.868(6)  
            U(1)-O(1)                      1.776(4)  
            U(1)-O(2)                      1.779(4)  
            U(1)-O(3)#2                    2.321(4)  
            U(1)-O(3)                      2.334(4)  
            U(1)-O(5)                      2.380(4)  
            U(1)-O(6)                      2.391(4)  
            U(1)-N(1)                      2.577(5)  
            U(1)-U(1)#2                    3.8853(4)  
            O(3)-U(1)#2                    2.321(4)  
            O(5)-S(1)                      1.520(4)  
            O(6)-S(2)                      1.538(5)  
            C(1)-N(1)                      1.156(7)  
            C(2)-N(2)                      1.132(7)  
            C(3)-S(1)                      1.769(7)  
            C(4)-S(1)                      1.776(6)  
            C(5)-S(2)                      1.748(12)  
            C(6)-S(2)                      1.712(11)  
   
            C(1)#1-Ni(1)-C(1)             92.2(3)  
            C(1)#1-Ni(1)-C(2)            176.6(3)  
            C(1)-Ni(1)-C(2)               89.5(2)  
            C(1)#1-Ni(1)-C(2)#1           89.5(2)  
            C(1)-Ni(1)-C(2)#1            176.6(3)  
            C(2)-Ni(1)-C(2)#1             89.0(3)  
            O(1)-U(1)-O(2)               175.37(18)  
            O(1)-U(1)-O(3)#2              91.29(17)  
            O(2)-U(1)-O(3)#2              93.06(18)  
            O(1)-U(1)-O(3)                89.74(17)  
            O(2)-U(1)-O(3)                93.45(18)  
            O(3)#2-U(1)-O(3)              66.83(15)  
            O(1)-U(1)-O(5)                91.51(17)  
            O(2)-U(1)-O(5)                87.94(17)  
            O(3)#2-U(1)-O(5)              76.46(13)  
            O(3)-U(1)-O(5)               143.29(13)  
            O(1)-U(1)-O(6)                89.15(17)  
            O(2)-U(1)-O(6)                88.49(18)  
            O(3)#2-U(1)-O(6)             140.94(14)  
            O(3)-U(1)-O(6)                74.12(13)  
! 169!
            O(5)-U(1)-O(6)               142.58(14)  
            O(1)-U(1)-N(1)                86.29(18)  
            O(2)-U(1)-N(1)                89.14(19)  
            O(3)#2-U(1)-N(1)             149.80(14)  
            O(3)-U(1)-N(1)               143.13(14)  
            O(5)-U(1)-N(1)                73.52(14)  
            O(6)-U(1)-N(1)                69.19(14)  
            O(1)-U(1)-U(1)#2              90.61(13)  
            O(2)-U(1)-U(1)#2              93.90(14)  
            O(3)#2-U(1)-U(1)#2            33.52(9)  
            O(3)-U(1)-U(1)#2              33.32(9)  
            O(5)-U(1)-U(1)#2             109.98(9)  
            O(6)-U(1)-U(1)#2             107.43(10)  
            N(1)-U(1)-U(1)#2             175.42(11)  
            U(1)#2-O(3)-U(1)             113.17(15)  
            S(1)-O(5)-U(1)               144.3(3)  
            S(2)-O(6)-U(1)               127.2(3)  
            N(1)-C(1)-Ni(1)              179.0(5)  
            N(2)-C(2)-Ni(1)              179.5(7)  
            O(5)-S(1)-C(3)               105.8(3)  
            O(5)-S(1)-C(4)               104.6(3)  
            C(3)-S(1)-C(4)                98.3(3)  
            O(6)-S(2)-C(6)               105.4(4)  
            O(6)-S(2)-C(5)               104.9(4)  
            C(6)-S(2)-C(5)               101.7(6)  
            C(1)-N(1)-U(1)               172.5(5)  
           _____________________________________________________________  
   
           Symmetry transformations used to generate equivalent atoms: 
           #1 -x+1,y,-z+1/2    #2 -x+1/2,-y+5/2,-z      
 
 
 
 
     
  
! 170!
Crystallographic Table  25.  Anisotropic displacement parameters (?
 2
 x 10
3
) for 
{(UO
2
)
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]}.  The anisotropic displacement factor exponent takes 
the form: -2 ? 
2
 [ h
2
 a*
2
 U11 + ... + 2 h k a* b* U12 ]  
   
    
_______________________________________________________________________  
   
              U11        U22        U33        U23        U13        U12  
    
_______________________________________________________________________  
   
    Ni(1)    14(1)      12(1)      29(1)       0         -1(1)       0  
    U(1)     17(1)      16(1)      24(1)       3(1)       2(1)       2(1)  
    O(1)     23(2)      33(2)      23(2)      -4(2)       7(2)       1(2)  
    O(2)     38(2)      32(2)      23(2)       3(2)       7(2)       0(2)  
    O(3)     17(2)      15(2)      47(2)       6(2)       2(2)      -1(1)  
    O(5)     27(2)      19(2)      33(2)       2(2)       9(2)      -2(1)  
    O(6)     23(2)      28(2)      46(3)       5(2)       9(2)      -1(2)  
    C(1)     19(2)      19(2)      34(3)       0(2)       4(2)      -5(2)  
    C(2)     22(3)      17(2)      47(4)      -2(2)       2(2)       4(2)  
    C(3)     40(4)      33(3)      48(4)      -1(3)      21(3)       7(3)  
    C(4)     42(4)      33(3)      41(4)      14(3)      22(3)      14(3)  
    C(5)     89(6)      80(5)     113(7)      34(5)      65(5)      28(4)  
    C(6)     89(6)      80(5)     113(7)      34(5)      65(5)      28(4)  
    S(1)     28(1)      20(1)      40(1)      -3(1)      13(1)      -4(1)  
    S(2)     29(1)      50(1)      38(1)       1(1)      10(1)       2(1)  
    N(1)     25(2)      19(2)      42(3)       3(2)       5(2)       4(2)  
    N(2)     25(3)      25(3)      82(5)     -15(3)       2(3)      -5(2)  
    
_______________________________________________________________________  
 
 
 
 
          
  
! 171!
Crystallographic Table 26.  Hydrogen coordinates ( x 10
4
) and isotropic 
         displacement parameters (?
 2
 x 10
3
) for {(UO
2
)
2
(DMSO)
4
(OH)
2
[Ni(CN)
4
]}. 
   
         ________________________________________________________________  
   
                               x                y                z           U(eq)  
         ________________________________________________________________  
   
          H(3A)        1501          9781          1279          59  
          H(3B)        2250          9870          2152          59  
          H(3C)        1754          8765          2261          59  
          H(4A)        3051          6824          1707          55  
          H(4B)        2663          7028          2512          55  
          H(4C)        3160          8134          2406          55  
          H(5A)        5448         10551          1671         129  
          H(5B)        5618         12072          1856         129  
          H(5C)        5793         11289           956         129  
          H(6A)        4364         13702          -430         129  
          H(6B)        5095         13323          -389         129  
          H(6C)        5000         13841           679         129  
         ________________________________________________________________  
 
  
! 172!
Crystallographic Table 27.  Crystal data and structure refinement for 
[Th(C
2
H
6
SO)
8
][Fe(CN)
6
] ?NO
3,
 Th8.  
   
   
      Identification code               Th8 
      Empirical formula                 C
22
 H
48
 Fe N
7
 O
11
 S
8
 Th  
      Formula weight                     1131.08  
      Temperature                        183(2) K 
      Wavelength                         0.71073 A 
      Crystal system, space group        Monoclinic,  P2
1
/n 
      Unit cel dimensions               a = 11.9796(9) ?   ? = 90 ? 
                                         b = 17.7389(13) ?    ? = 90.117(2) ? 
                                         c = 20.0389(15) ?   ? = 90 ?  
        Volume                             4258.4(5) ?
3
   
        Z, Calculated density              4,  3.446 Mg/m
3
 
        Absorption coeficient             4.276 mm
-1
 
        F(000)                             3920  
        Crystal size                       0.10 x 0.10 x 0.10 mm 
        Theta range for data collection    1.53 to 28.31 deg.  
        Limiting indices                   -15<=h<=15, -23<=k<=23, -26<=l<=26  
        Reflections collected / unique     43457 / 10579 [R(int) = 0.0690]  
        Completenes to theta = 28.31     99.8 %  
        Absorption correction              None 
        Max. and min. transmision        0.2261 and 0.2261  
        Refinement method                  Full-matrix least-squares on F
2
 
        Data / restraints / parameters     10579 / 0 / 452  
        Goodnes-of-fit on F^2             1.111  
        Final R indices [I>2sigma(I)]     R1 = 0.0840, wR2 = 0.2100  
        R indices (al data)               R1 = 0.1029, wR2 = 0.2164  
        Largest dif. peak and hole       9.836 and -2.858 e.?
-3
 
 
! 173!
 
Crystallographic Table 28.  Atomic coordinates ( x 10
4
) and equivalent isotropic 
displacement parameters (?
2
 x 10
3
) for [Th(C
2
H
6
SO)
8
][Fe(CN)
6
]
.
NO
3
 .         
U(eq) is defined as one third of      the trace of the orthogonalized Uij tensor. 
 
          
   
         ________________________________________________________________  
   
                          x             y                   z           U(eq)  
         ________________________________________________________________  
   
          Th(1)         7548(1)       2367(1)        935(1)       19(1)  
          Fe(1)         7372(2)        878(1)      -1612(1)       23(1)  
          S(1)           6844(3)        384(2)       1220(2)       29(1)  
          O(1)          7600(8)       1011(5)        965(5)        29(2)  
          C(1)          5757(11)       955(8)      -1711(7)       30(3)  
          N(1)          4803(11)      1001(8)      -1775(7)      46(3)  
          N(2)          7303(10)      1761(6)       -278(5)       31(2)  
          N(3)          9921(10)       747(9)      -1586(8)       53(4)  
          N(4)          7463(11)        -2(7)      -2944(6)        41(3)  
          N(5)          7662(12)      2377(8)      -2404(8)     54(4)  
          N(6)          7200(13)      -623(8)       -805(6)       47(3)  
          N(7)          7335(18)      6041(9)        709(9)       62(4)  
          S(2)           4765(3)       2705(2)        348(2)        37(1)  
          O(2)          5582(7)       2180(6)        722(5)        35(2)  
          C(2)          7315(10)      1441(7)       -777(6)       25(2)  
          O(3)          7174(10)      3327(6)        135(5)       40(2)  
          C(3)          8999(12)       815(8)      -1587(7)        37(3)  
          S(3)          7015(6)       3602(4)       -567(3)         83(2)  
          O(4)         6541(9)       3381(6)       1494(5)        40(2)  
          C(4)          7424(11)       322(7)      -2447(6)        28(3)  
          S(4)          6707(3)       4228(2)       1459(2)        37(1)  
          O(5)         6595(9)       1903(6)       1936(5)       42(3)  
          C(5)         7512(11)      1826(8)      -2095(6)       28(3)  
          S(5)         5443(3)       2130(2)       2197(2)        37(1)  
          O(6)         8968(9)       2030(6)       1739(6)        46(3)  
          C(6)         7254(12)       -69(8)      -1110(7)        34(3)  
          S(6)         9180(4)       1467(2)       2287(2)        44(1)  
          O(7)         9306(9)       2256(6)        357(6)        44(3)  
          C(7)         7511(11)      -457(7)        964(7)       27(2)  
          S(7)         9791(5)       1865(3)       -244(3)       67(1)  
          O(8)         8746(8)       3454(6)       1220(6)       47(3)  
          C(8)         5714(12)       362(9)        631(8)        39(3)  
          S(8)         9816(4)       3787(2)        955(2)        49(1)  
          C(9)         4242(14)      2116(11)      -294(7)      47(4)  
! 174!
          O(9)         7583(17)      5917(8)       1287(8)       87(5)  
          C(10)        3544(14)      2720(12)       858(9)       56(5)  
          O(10)        8020(20)      6089(12)       281(12)     118(7)  
          C(11)        9290(20)      2069(14)      3016(9)       75(6)  
          O(11)        6360(16)      6028(10)       504(9)       88(5)  
          C(12)       10630(14)      1223(11)      2209(10)      57(5)  
          C(13)        5717(17)      2375(12)      3038(8)       58(5)  
          C(14)        4737(15)      1248(9)       2303(9)       48(4)  
          C(15)        6890(30)      4591(13)      -487(11)     130(15)  
          C(16)        7950(30)      3679(17)      -620(20)     280(40)  
          C(17)        5311(17)      4589(12)      1499(12)      68(6)  
          C(18)        7198(18)      4501(10)      2275(8)       54(5)  
          C(19)       10883(15)      3416(10)      1451(10)      54(4)  
          C(20)        9860(18)      4696(11)      1283(16)      98(10)  
          C(21)        9920(20)       884(11)        84(17)     108(12)  
          C(22)       11165(13)      2077(10)      -260(9)       50(4)  
         ________________________________________________________________  
 
! 175!
 
Crystallographic Table 29.  Bond lengths [?] and angles [?] for, 
[Th(C
2
H
6
SO)
8
][Fe(CN)
6
]
.
NO
3
.  
           _____________________________________________________________  
   
            Th(1)-O(3)                     2.379(10)  
            Th(1)-O(1)                    2.407(9)  
            Th(1)-O(7)                     2.413(10)  
            Th(1)-O(2)                     2.415(9)  
            Th(1)-O(6)                     2.416(10)  
            Th(1)-O(4)                     2.439(9)  
            Th(1)-O(5)                     2.453(10)  
            Th(1)-O(8)                     2.470(10)  
            Th(1)-N(2)                     2.674(11)  
            Fe(1)-C(4)                     1.944(13)  
            Fe(1)-C(5)                     1.947(13)  
            Fe(1)-C(1)                     1.950(14)  
            Fe(1)-C(2)                     1.950(12)  
            Fe(1)-C(3)                     1.952(15)  
            Fe(1)-C(6)                     1.964(15)  
            S(1)-O(1)                      1.523(9)  
            S(1)-C(7)                      1.770(12)  
            S(1)-C(8)                      1.795(14)  
            C(1)-N(1)                      1.152(18)  
            N(2)-C(2)                      1.149(16)  
            N(3)-C(3)                      1.111(18)  
            N(4)-C(4)                      1.150(17)  
            N(5)-C(5)                      1.172(19)  
            N(6)-C(6)                      1.158(19)  
            N(7)-O(10)                     1.19(2)  
            N(7)-O(9)                      1.22(2)  
            N(7)-O(11)                     1.24(2)  
            S(2)-O(2)                      1.544(10)  
            S(2)-C(9)                      1.771(15)  
            S(2)-C(10)                     1.787(17)  
            O(3)-S(3)                      1.502(11)  
            O(3)-C(16)                     1.88(4)  
            S(3)-C(16)                     1.14(3)  
            S(3)-C(15)                     1.77(2)  
            O(4)-S(4)                      1.517(11)  
            S(4)-C(17)                     1.792(19)  
            S(4)-C(18)                     1.802(16)  
            O(5)-S(5)                      1.530(11)  
            S(5)-C(13)                     1.770(16)  
            S(5)-C(14)                     1.793(16)  
            O(6)-S(6)                      1.506(11)  
! 176!
            S(6)-C(12)                     1.797(17)  
            S(6)-C(11)                     1.81(2)  
            O(7)-S(7)                      1.508(12)  
            S(7)-C(22)                     1.689(17)  
            S(7)-C(21)                     1.87(2)  
            O(8)-S(8)                      1.509(12)  
            S(8)-C(20)                     1.742(19)  
            S(8)-C(19)                     1.747(17)  
   
            O(3)-Th(1)-O(1)              137.4(3)  
            O(3)-Th(1)-O(7)               84.2(4)  
            O(1)-Th(1)-O(7)               84.7(3)  
            O(3)-Th(1)-O(2)               78.3(4)  
            O(1)-Th(1)-O(2)               83.8(3)  
            O(7)-Th(1)-O(2)              139.1(4)  
            O(3)-Th(1)-O(6)              139.3(4)  
            O(1)-Th(1)-O(6)               73.6(3)  
            O(7)-Th(1)-O(6)               71.7(4)  
            O(2)-Th(1)-O(6)              140.2(4)  
            O(3)-Th(1)-O(4)               71.9(3)  
            O(1)-Th(1)-O(4)              137.5(3)  
            O(7)-Th(1)-O(4)              135.5(4)  
            O(2)-Th(1)-O(4)               72.5(3)  
            O(6)-Th(1)-O(4)              103.0(4)  
            O(3)-Th(1)-O(5)              134.7(4)  
            O(1)-Th(1)-O(5)               69.9(3)  
            O(7)-Th(1)-O(5)              140.6(4)  
            O(2)-Th(1)-O(5)               69.1(4)  
            O(6)-Th(1)-O(5)               72.5(4)  
            O(4)-Th(1)-O(5)               68.9(3)  
            O(3)-Th(1)-O(8)               72.9(4)  
            O(1)-Th(1)-O(8)              139.4(3)  
            O(7)-Th(1)-O(8)               70.6(4)  
            O(2)-Th(1)-O(8)              135.6(3)  
            O(6)-Th(1)-O(8)               68.3(4)  
            O(4)-Th(1)-O(8)               66.8(3)  
            O(5)-Th(1)-O(8)              110.1(4)  
            O(3)-Th(1)-N(2)               69.9(3)  
            O(1)-Th(1)-N(2)               67.9(3)  
            O(7)-Th(1)-N(2)               68.0(4)  
            O(2)-Th(1)-N(2)               71.3(3)  
            O(6)-Th(1)-N(2)              125.7(4)  
            O(4)-Th(1)-N(2)              131.3(4)  
            O(5)-Th(1)-N(2)              123.9(4)  
            O(8)-Th(1)-N(2)              126.0(4)  
            C(4)-Fe(1)-C(5)               90.4(5)  
! 177!
            C(4)-Fe(1)-C(1)               88.9(5)  
            C(5)-Fe(1)-C(1)               88.6(6)  
            C(4)-Fe(1)-C(2)              179.6(6)  
            C(5)-Fe(1)-C(2)               89.3(5)  
            C(1)-Fe(1)-C(2)               90.9(5)  
            C(4)-Fe(1)-C(3)               87.7(5)  
            C(5)-Fe(1)-C(3)               88.6(6)  
            C(1)-Fe(1)-C(3)              175.6(6)  
            C(2)-Fe(1)-C(3)               92.5(5)  
            C(4)-Fe(1)-C(6)               90.5(6)  
            C(5)-Fe(1)-C(6)              178.8(6)  
            C(1)-Fe(1)-C(6)               92.2(6)  
            C(2)-Fe(1)-C(6)               89.8(5)  
            C(3)-Fe(1)-C(6)               90.6(6)  
            O(1)-S(1)-C(7)               104.4(6)  
            O(1)-S(1)-C(8)               104.1(6)  
            C(7)-S(1)-C(8)                97.5(7)  
            S(1)-O(1)-Th(1)              136.2(5)  
            N(1)-C(1)-Fe(1)              179.4(14)  
            C(2)-N(2)-Th(1)              170.9(11)  
            O(10)-N(7)-O(9)              122(2)  
            O(10)-N(7)-O(11)             114(2)  
            O(9)-N(7)-O(11)              123(2)  
            O(2)-S(2)-C(9)               102.7(7)  
            O(2)-S(2)-C(10)              104.5(7)  
            C(9)-S(2)-C(10)               97.8(9)  
            S(2)-O(2)-Th(1)              128.3(6)  
            N(2)-C(2)-Fe(1)              178.2(12)  
            S(3)-O(3)-C(16)               37.2(6)  
            S(3)-O(3)-Th(1)              152.5(6)  
            C(16)-O(3)-Th(1)             133.1(12)  
            N(3)-C(3)-Fe(1)              176.8(14)  
            C(16)-S(3)-O(3)               89.7(17)  
            C(16)-S(3)-C(15)              88(2)  
            O(3)-S(3)-C(15)              104.4(9)  
            S(4)-O(4)-Th(1)              130.1(6)  
            N(4)-C(4)-Fe(1)              179.2(14)  
            O(4)-S(4)-C(17)              103.3(8)  
            O(4)-S(4)-C(18)              105.5(7)  
            C(17)-S(4)-C(18)              99.6(10)  
            S(5)-O(5)-Th(1)              127.8(6)  
            N(5)-C(5)-Fe(1)              175.4(13)  
            O(5)-S(5)-C(13)              103.0(8)  
            O(5)-S(5)-C(14)              103.7(7)  
            C(13)-S(5)-C(14)             100.9(9)  
            S(6)-O(6)-Th(1)              140.2(7)  
! 178!
            N(6)-C(6)-Fe(1)              178.7(14)  
            O(6)-S(6)-C(12)              105.0(8)  
            O(6)-S(6)-C(11)              102.0(9)  
            C(12)-S(6)-C(11)              98.4(11)  
            S(7)-O(7)-Th(1)              139.4(7)  
            O(7)-S(7)-C(22)             106.9(8)  
            O(7)-S(7)-C(21)              100.3(10)  
            C(22)-S(7)-C(21)              97.8(10)  
            S(8)-O(8)-Th(1)              135.9(7)  
            O(8)-S(8)-C(20)              104.7(11)  
            O(8)-S(8)-C(19)              105.8(8)  
            C(20)-S(8)-C(19)              96.4(9)  
            S(3)-C(16)-O(3)               53.0(18)  
           _____________________________________________________________  
   
             
 
! 179!
 Crystallographic Table 30.  Anisotropic displacement parameters (A
2
 x 10
3
) for 
[Th(C
2
H
6
SO)
8
][Fe(CN)
6
]
.
NO
3
. The anisotropic displacement factor exponent takes the 
form: -2 ?^2 [ h^2 a*^2 U11 + ... + 2 h k a* b* U12 ]     
_______________________________________________________________________  
   
              U11        U22        U33        U23        U13        U12  
    
_______________________________________________________________________  
   
    Th(1)    20(1)      19(1)      18(1)      -2(1)       1(1)       0(1)  
    Fe(1)    27(1)      24(1)      18(1)      -3(1)       1(1)       0(1)  
    S(1)     30(2)      28(2)      27(2)       0(1)       3(1)       2(1)  
    O(1)     34(5)      21(4)      32(5)      -3(4)       5(4)       0(4)  
    C(1)     30(7)      33(7)      28(6)      -2(5)       0(5)      -3(5)  
    N(1)     34(7)      52(8)      52(8)       7(6)      -6(6)      -7(6)  
    N(2)     42(7)      28(6)      23(5)      -3(4)       2(5)      -3(5)  
    N(3)     24(6)      71(10)     65(10)    -13(8)      -2(6)       3(6)  
    N(4)     51(8)      40(7)      32(6)     -11(5)       0(6)       9(6)  
    N(5)     48(8)      37(7)      76(10)     10(7)     -23(7)      -1(6)  
    N(6)     70(10)     35(7)      36(7)      -1(6)      -1(6)       2(7)  
    N(7)     99(14)     34(8)      52(10)     -6(7)      12(10)     11(8)  
    S(2)     29(2)      39(2)      42(2)      -2(2)      -1(1)       1(1)  
    O(2)     21(4)      43(6)      42(5)      -5(4)      -3(4)      -2(4)  
    C(2)     31(6)      26(6)      19(6)       4(5)       3(5)       1(5)  
    O(3)     66(7)      31(5)      22(4)       2(4)       6(5)       3(5)  
    C(3)     41(8)      39(8)      30(7)     -14(6)      -8(6)      15(6)  
    S(3)    111(5)      93(5)      45(3)      16(3)      20(3)      17(4)  
    O(4)     44(6)      32(5)      44(6)      -9(4)      23(5)      -1(4)  
    C(4)     27(6)      30(7)      27(6)      -2(5)      -5(5)       3(5)  
    S(4)     48(2)      31(2)      33(2)      -2(1)       9(2)       4(2)  
    O(5)     55(7)      40(6)      31(5)       0(4)      20(5)      -1(5)  
    C(5)     30(6)      31(7)      22(6)       4(5)       3(5)       0(5)  
    S(5)     39(2)      38(2)      35(2)       5(2)      12(2)       4(2)  
    O(6)     46(6)      44(6)      49(6)       3(5)     -24(5)      -1(5)  
    C(6)     39(8)      36(8)      26(6)      -3(6)       5(5)       2(6)  
    S(6)     50(2)      41(2)      40(2)       7(2)      -7(2)     -12(2)  
    O(7)     33(5)      46(7)      51(6)      -5(5)      15(5)       2(5)  
    C(7)     28(6)      18(6)      34(6)      -3(5)       4(5)       1(5)  
    S(7)     63(3)      66(3)      71(3)      -3(3)       5(3)       3(3)  
    O(8)     30(5)      29(5)      80(8)     -12(5)      -5(5)      -1(4)  
    C(8)     28(7)      38(8)      50(9)      10(7)     -11(6)      -1(6)  
    S(8)     41(2)      46(2)      60(3)       6(2)      -5(2)     -13(2)  
    C(9)     48(9)      67(11)     27(7)      -8(7)     -13(6)       4(8)  
    O(9)    143(16)     51(9)      68(10)      2(7)      32(10)     13(9)  
    C(10)    38(8)      88(14)     42(9)     -10(9)       5(7)      15(9)  
    O(10)   140(19)     92(14)    121(17)     31(12)     34(15)     -6(13)  
! 180!
    C(11)   108(18)     87(16)     31(9)      -2(9)       2(10)     -2(14)  
    O(11)    89(12)     90(12)     84(11)     -6(9)     -13(10)     29(10)  
    C(12)    37(9)      58(11)     76(13)     11(10)      1(8)       4(8)  
    C(13)    62(11)     83(14)     29(7)     -11(8)      -6(7)      10(10)  
    C(14)    52(10)     35(8)      57(10)      3(7)      19(8)      -4(7)  
    C(15)   270(40)     66(15)     57(13)     35(12)     70(20)     80(20)  
    C(16)   200(30)    180(30)    460(60)    280(40)   -320(40)   -190(30)  
    C(17)    65(13)     54(12)     86(15)     -4(11)      8(11)     19(10)  
    C(18)    93(14)     41(9)      29(8)       0(7)      -6(8)       6(9)  
    C(19)    51(10)     46(10)     64(11)     -2(8)     -14(9)       2(8)  
    C(20)    63(13)     36(10)    200(30)    -30(14)    -73(16)      6(9)  
    C(21)    81(15)     33(10)    210(30)      2(14)     97(19)     -7(10)  
    C(22)    38(8)      51(10)     62(11)     -4(8)      18(8)       1(7)  
    
_______________________________________________________________________  
 
! 181!
 
         Crystallographic Table 31.  Hydrogen coordinates ( x 10
4
) and isotropic 
         displacement parameters (A
2
 x 10
3
) for  [Th(C
2
H
6
SO)
8
][Fe(CN)
6
]
.
NO
3
.  
   
         ________________________________________________________________  
   
                          x             y             z           U(eq)  
         ________________________________________________________________  
   
          H(7A)        8180          -540          1237          40  
          H(7B)        7726          -414           494          40  
          H(7C)        6998          -883          1019          40  
          H(8A)        5228           798           703          58  
          H(8B)        5283          -103           692          58  
          H(8C)        6014           377           177          58  
          H(9A)        4820          2041          -633          71  
          H(9B)        3587          2353          -500          71  
          H(9C)        4028          1627          -105          71  
          H(10A)       3687          3026          1257          84  
          H(10B)       3353          2205           992          84  
          H(10C)       2922          2939           605          84  
          H(11A)       8544          2260          3133         113  
          H(11B)       9782          2495          2918         113  
          H(11C)       9590          1780          3391         113  
          H(12A)      10730           891          1823          85  
          H(12B)      10878           961          2614          85  
          H(12C)      11073          1682          2148          85  
          H(13A)       6106          2861          3053          87  
          H(13B)       6185          1987          3244          87  
          H(13C)       5011          2414          3281          87  
          H(14A)       4530          1045          1865          72  
          H(14B)       4062          1324          2570          72  
          H(14C)       5232           891          2531          72  
          H(15A)       6199          4712          -249         195  
          H(15B)       6871          4821          -932         195  
          H(15C)       7530          4787          -237         195  
          H(16A)       8305          3191          -703         424  
          H(16B)       8253          3890          -200         424  
          H(16C)       8113          4025          -985         424  
          H(17A)       4927          4490          1076         103  
          H(17B)       5335          5134          1580         103  
          H(17C)       4909          4341          1864         103  
          H(18A)       7976          4341          2329          81  
          H(18B)       6737          4260          2617          81  
          H(18C)       7149          5050          2321          81  
          H(19A)      11002          2886          1334          81  
! 182!
          H(19B)      10673          3454          1922          81  
          H(19C)      11573          3701          1374          81  
          H(20A)       9299          5010          1060         148  
          H(20B)      10603          4912          1212         148 
          H(20C)       9702          4677          1763         148  
          H(21A)       9172           666           137         163  
          H(21B)      10298           894           517         163  
          H(21C)      10350           578          -230         163  
          H(22A)      11267          2582          -449          76  
          H(22B)      11560          1707          -536          76  
          H(22C)      11466          2065           195          76  
         ________________________________________________________________ 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
! 183!
Crystallographic Table 32.  Crystal data and structure refinement for 
[Th(C
2
H
6
SO)
9
][Pt(CN)
4
]
2
?4H
2
O, Th7.  
   
   
        Identification code               Th7 
        Empirical formula                  C
40
 H
96
 N
8
 O
16
 Pt
4
 S
16
 Th
2
 
        Formula weight                     2702.65  
        Temperature                        293(2) K 
        Wavelength                         0.71073 A 
        Crystal system, space group        Triclinic,  P-1  
        Unit cel dimensions               a = 12.4199(6) A  ? = 102.0800(10)   
                                         b = 20.3265(10) A   ? = 98.2710(10) 
                                         c = 21.1132(10) A   ? = 96.6940(10)  
        Volume                             5098.3(4) A
3
 
        Z, Calculated density              2,  1.761 Mg/m
3
 
        Absorption coeficient             8.745 mm
-1
 
        F(000)                             2536  
        Crystal size                       0.01 x 0.01 x 0.01 mm  
        Theta range for data collection    1.00 to 28.32 deg.  
        Limiting indices                   -16<=h<=16, -27<=k<=21, -28<=l<=28  
        Reflections collected / unique     43789 / 23889 [R(int) = 0.0646]  
        Completenes to theta = 28.32      94.0 %  
        Absorption correction              None 
        Refinement method                 Full-matrix least-squares on F
2
 
        Data / restraints / parameters     23889 / 0 / 1031  
        Goodnes-of-fit on F^2             0.975  
        Final R indices [I>2sigma(I)]     R1 = 0.0582, wR2 = 0.1214  
        R indices (al data)               R1 = 0.1013, wR2 = 0.1447  
        Largest dif. peak and hole        2.651 and -1.963 e.A
-3
 
 
! 184!
 
         Crystallographic Table 33.  Atomic coordinates ( x 10
4
) and equivalent isotropic 
         displacement parameters (A
2
 x 10
3
) for [Th(C
2
H
6
SO)
9
][Pt(CN)
4
]
2
?4H
2
O.  
         U(eq) is defined as one third of the trace of the orthogonalized  
         Uij tensor.  
   
         ________________________________________________________________  
   
                         x             y             z           U(eq)  
         ________________________________________________________________  
   
          Th(1)        4891(1)       7335(1)       2610(1)       24(1)  
          Pt(1)        3634(1)        396(1)        917(1)       32(1)  
          O(1)         4232(5)       7950(4)       3604(4)       32(2)  
          N(1)         9648(10)      7162(7)        757(7)       67(4)  
          O(1W)          56(12)      5711(10)      3913(8)      105(7)  
          Th(2)        9886(1)       2346(1)       2368(1)       22(1)  
          Pt(2)        1326(1)       9159(1)       4251(1)       37(1)  
          O(2)         5334(6)       6876(4)       3568(4)       33(2)  
          N(2)         7300(10)      4264(7)        771(7)       67(4)  
          O(2W)        4386(16)      3360(9)       1226(11)     132(9)  
          Pt(3)        6097(1)       4069(1)       4141(1)       32(1)  
          O(3)         5944(5)       8476(4)       3101(4)       35(2)  
          N(3)         5681(10)       379(6)       1956(6)       64(4)  
          O(3W)        4970(30)       730(20)      3738(18)     131(19)  
          Pt(4)        8438(1)       5726(1)        756(1)       34(1)  
          O(4)         5738(6)       7669(4)       1734(4)       40(2)  
          O(4W)        9070(30)      8505(16)      1388(17)      75(14)  
          O(5)         6910(6)       7282(4)       2838(3)       33(2)  
          O(6)         5299(6)       6201(4)       2189(4)       34(2)  
          S(7)         6035(2)       6360(1)       3766(1)       31(1)  
          O(7)         3717(5)       6791(4)       1538(3)       27(2)  
          S(8)         7618(2)       6902(2)       2393(2)       44(1)  
          O(8)         3204(6)       6695(4)       2746(3)       34(2)  
          S(9)         2812(2)       6599(2)       3377(1)       31(1)  
          O(9)         3614(6)       8075(4)       2304(3)       31(2)  
          S(10)       10915(2)       1435(1)       3576(1)       28(1)  
          C(10)        7110(10)      6877(6)       4389(6)       47(3)  
          S(11)        5391(2)       7770(2)       1045(2)       38(1)  
          O(11)       11782(5)       2199(4)       2639(3)       30(2)  
          C(11)        5262(9)       5992(6)       4262(5)       39(3)  
          S(12)        9335(2)        582(1)       1549(1)       31(1)  
          O(12)       10892(5)       3193(4)       1914(3)       28(2)  
          C(12)        2362(9)       7085(6)        609(5)       34(3)  
          S(13)        8167(2)       3672(2)       2697(2)       36(1)  
          O(13)       10523(5)       1828(4)       1328(3)       27(2)  
! 185!
          C(13)        2251(9)       5725(5)       3178(6)       34(3)  
          S(14)        4985(2)       8248(2)       4255(2)       38(1)  
          O(14)       10463(6)       3355(4)       3269(3)       33(2)  
          S(15)       10318(2)       2093(2)        711(1)       30(1)  
          O(15)       10249(5)       1984(4)       3404(3)       25(2)  
          S(16)        2476(2)       6754(1)       1331(1)       30(1)  
          O(16)        8225(5)       2216(4)       2828(3)       30(2)  
          S(17)        7112(2)       8791(2)       3083(2)       37(1)  
          O(17)        8410(5)       1916(4)       1449(4)       34(2)  
          S(18)        4701(2)       5569(1)       1683(1)       33(1)  
          O(18)        8750(5)       3252(4)       2207(3)       28(2)  
          S(19)        2834(3)       8495(2)       2635(2)       43(1)  
          O(19)        9641(6)       1121(4)       2203(4)       32(2)  
          S(20)       10837(2)       3941(1)       1912(2)       34(1)  
          S(21)        7855(2)       1806(2)       3320(2)       35(1)  
          S(25)        7164(2)       1890(2)       1292(1)       30(1)  
          S(31)       12662(2)       1940(2)       2246(2)       41(1)  
          N(41)        -274(9)       7880(7)       4318(6)       63(4)  
          C(51)        7195(9)       3844(6)       4814(6)       35(3)  
          C(52)        5004(10)      3272(7)       4160(5)       37(3)  
          N(52)        4356(10)      2825(6)       4144(6)       62(3)  
          C(55)        7708(9)       4798(7)        756(6)       38(3)  
          C(56)        7318(10)      5781(6)         -3(7)       42(3)  
          C(59)        2364(9)        347(6)        196(6)       35(3)  
          N(59)        1631(9)        356(6)       -187(6)       58(3)  
          C(60)        7171(9)       4858(7)       4145(6)       38(3)  
          C(61)        5021(9)       4324(6)       3484(6)       35(3)  
          N(61)        4378(9)       1917(6)        905(6)       58(3)  
          N(62)        2934(10)     -1152(6)        850(5)       57(3)  
          C(62)        2216(10)      9138(7)       5108(7)       47(3)  
          N(63)        6687(9)       5831(6)       -430(5)       46(3)  
          C(63)         302(10)      8326(7)       4270(6)       41(3)  
          C(64)        9225(10)      6635(8)        739(7)       54(4)  
          N(65)        7830(9)       5318(6)       4140(6)       57(3)  
          C(65)        3176(10)      -562(7)        896(5)       39(3)  
          N(66)        4341(8)       4484(5)       3135(5)       45(3)  
          C(66)        4095(10)      1368(7)        919(7)       46(3)  
          N(67)        7821(9)       3730(6)       5224(5)       57(3)  
          C(67)        4921(9)        395(6)       1584(6)       33(3)  
          C(68)        2339(11)      9951(8)       4213(6)       50(4)  
          N(68)        2729(9)       9140(6)       5592(5)       57(3)  
          N(69)        2985(10)     10454(7)       4216(8)       75(4)  
          C(70)       10028(9)        932(6)       3944(6)       43(3)  
          C(71)       11645(8)       2219(7)        492(6)       43(3)  
          C(80)        2012(10)      5902(6)        935(5)       40(3)  
          C(81)        1558(9)       6947(6)       3351(7)       45(3)  
! 186!
          C(82)        5149(10)      5656(6)        949(5)       41(3)  
          C(84)        6724(9)       1063(6)        789(6)       41(3)  
          C(85)        9734(10)      1344(6)         83(6)       46(3)  
          C(86)       11868(9)       1870(6)       4295(6)       42(3)  
          C(87)        6752(9)       3504(7)       2314(7)       58(4)  
          C(88)        6984(9)       2363(6)        678(6)       45(3)  
          C(89)        8238(10)      2388(7)       4112(5)       48(3)  
          C(90)        6417(9)       1796(7)       3214(6)       50(4)  
          S(99)       11012(3)       3568(2)       3986(1)       38(1)  
          N(100)        -68(10)      9246(6)       2919(6)       61(3)  
          N(101)      10196(10)      5616(6)       1932(6)       64(3)  
          C(201)       9543(10)      5683(6)       1512(6)       40(3)  
          C(202)        448(11)      9202(7)       3400(8)       53(4)  
          C(301)       8780(10)      7496(7)       2431(6)       52(4)  
          C(302)       7810(9)       8920(7)       3891(6)       46(3)  
          C(303)       4823(10)      9115(6)       4448(6)       46(3)  
          C(304)      12178(9)       4254(6)       1838(7)       47(3)  
          C(305)      10540(9)        191(6)       1511(7)       48(3)  
          C(306)       5464(10)      4925(6)       1864(7)       52(4)  
          C(307)      10149(10)      3925(7)       1112(6)       50(3)  
          C(308)       3392(13)      9337(6)       2668(6)       63(4)  
          C(309)       6996(10)      9641(6)       3069(7)       55(4)  
          C(310)       8437(11)      4514(6)       2599(7)       57(4)  
          C(311)      13671(10)      2652(7)       2354(6)       59(4)  
          C(312)       1673(10)      8400(8)       1998(7)       65(4)  
          C(313)      13381(10)      1466(7)       2738(6)       52(4)  
          C(314)       4240(13)      7961(7)       4843(7)       65(4)  
          C(315)       5704(13)      8648(7)       1109(9)       81(5)  
          C(316)       6462(15)      7515(10)       641(7)       99(7)  
          C(317)      12242(11)      4057(9)       4000(8)       80(5)  
          C(318)      10330(12)      4235(10)      4323(9)      110(8)  
          C(319)       8457(10)       -62(6)       1756(6)       43(3)  
          C(501)       8292(12)      6420(8)       2876(6)       68(5)  
         ________________________________________________________________  
 
! 187!
 
Crystallographic Table 34.  Bond lengths [A] and angles [?] for 
[Th(C
2
H
6
SO)
9
][Pt(CN)
4
]
2
?4H
2
O.  
           _____________________________________________________________  
   
            Th(1)-O(2)                    2.420(7)  
            Th(1)-O(8)                    2.421(7)  
            Th(1)-O(9)                    2.422(6)  
            Th(1)-O(6)                    2.429(7)  
            Th(1)-O(4)                    2.429(8)  
            Th(1)-O(3)                    2.462(7)  
            Th(1)-O(7)                    2.469(7)  
            Th(1)-O(1)                    2.504(7)  
            Th(1)-O(5)                    2.504(7)  
            Pt(1)-C(65)                   1.954(13)  
            Pt(1)-C(67)                   1.973(12)  
            Pt(1)-C(66)                   1.992(14)  
            Pt(1)-C(59)                   2.006(11)  
            O(1)-S(14)                    1.511(8)  
            N(1)-C(64)                    1.128(17)  
            Th(2)-O(17)                   2.404(7)  
            Th(2)-O(11)                   2.412(6)  
            Th(2)-O(16)                   2.414(7)  
            Th(2)-O(19)                   2.417(7)  
            Th(2)-O(12)                   2.446(7)  
            Th(2)-O(14)                   2.445(7)  
            Th(2)-O(15)                   2.450(6)  
            Th(2)-O(18)                   2.495(6)  
            Th(2)-O(13)                   2.505(7)  
            Pt(2)-C(68)                   1.947(17)  
            Pt(2)-C(202)                  1.986(14)  
            Pt(2)-C(62)                   1.992(12)  
            Pt(2)-C(63)                   2.008(14)  
            O(2)-S(7)                     1.524(7)  
            N(2)-C(55)                    1.152(15)  
            Pt(3)-C(60)                   1.960(13)  
            Pt(3)-C(61)                   1.977(12)  
            Pt(3)-C(51)                   1.987(13)  
            Pt(3)-C(52)                   2.000(14)  
            O(3)-S(17)                    1.526(7)  
            N(3)-C(67)                    1.146(14)  
            Pt(4)-C(201)                  1.974(12)  
            Pt(4)-C(56)                   1.996(13)  
            Pt(4)-C(55)                   1.996(14)  
            Pt(4)-C(64)                   1.997(16)  
            O(4)-S(11)                    1.521(8)  
! 188!
            O(5)-S(8)                     1.532(7)  
            O(6)-S(18)                    1.522(8)  
            S(7)-C(11)                    1.741(11)  
            S(7)-C(10)                    1.791(10)  
            O(7)-S(16)                    1.529(7)  
            S(8)-C(301)                   1.751(13)  
            S(8)-C(501)                   1.750(13)  
            O(8)-S(9)                     1.524(7)  
            S(9)-C(13)                    1.771(11)  
            S(9)-C(81)                    1.782(10)  
            O(9)-S(19)                    1.515(7)  
            S(10)-O(15)                   1.536(7)  
            S(10)-C(86)                   1.780(11)  
            S(10)-C(70)                   1.783(12)  
            S(11)-C(315)                  1.754(14)  
            S(11)-C(316)                  1.752(14)  
            O(11)-S(31)                   1.540(7)  
            S(12)-O(19)                   1.539(8)  
            S(12)-C(319)                  1.772(12)  
            S(12)-C(305)                  1.779(11)  
            O(12)-S(20)                   1.531(7)  
            C(12)-S(16)                   1.784(10)  
            S(13)-O(18)                   1.522(7)  
            S(13)-C(310)                  1.766(12)  
            S(13)-C(87)                   1.787(11)  
            O(13)-S(15)                   1.512(7)  
            S(14)-C(303)                  1.767(12)  
            S(14)-C(314)                  1.800(14)  
            O(14)-S(99)                   1.517(7)  
            S(15)-C(71)                   1.778(10)  
            S(15)-C(85)                   1.795(11)  
            S(16)-C(80)                   1.748(12)  
            O(16)-S(21)                   1.547(7)  
            S(17)-C(302)                  1.751(11)  
            S(17)-C(309)                  1.756(13)  
            O(17)-S(25)                   1.528(7)  
            S(18)-C(82)                   1.755(10)  
            S(18)-C(306)                  1.775(10)  
            S(19)-C(308)                  1.755(14)  
            S(19)-C(312)                  1.786(13)  
            S(20)-C(304)                  1.754(11)  
            S(20)-C(307)                  1.772(12)  
            S(21)-C(90)                   1.766(11)  
            S(21)-C(89)                   1.799(12)  
            S(25)-C(84)                   1.767(12)  
            S(25)-C(88)                   1.773(11)  
! 189!
            S(31)-C(311)                  1.752(13)  
            S(31)-C(313)                  1.778(12)  
            N(41)-C(63)                   1.118(15)  
            C(51)-N(67)                   1.158(14)  
            C(52)-N(52)                   1.133(15)  
            C(56)-N(63)                   1.135(14)  
            C(59)-N(59)                   1.132(14)  
            C(60)-N(65)                   1.172(15)  
            C(61)-N(66)                   1.160(14)  
            N(61)-C(66)                   1.137(15)  
            N(62)-C(65)                   1.182(15)  
            C(62)-N(68)                   1.123(15)  
            C(68)-N(69)                   1.221(18)  
            S(99)-C(317)                  1.717(14)  
            S(99)-C(318)                  1.760(16)  
            N(100)-C(202)                 1.147(16)  
            N(101)-C(201)                 1.153(14)  
   
            O(2)-Th(1)-O(8)              73.2(2)  
            O(2)-Th(1)-O(9)             134.4(2)  
            O(8)-Th(1)-O(9)              81.1(2)  
            O(2)-Th(1)-O(6)              74.7(2)  
            O(8)-Th(1)-O(6)              82.2(3)  
            O(9)-Th(1)-O(6)             138.4(2)  
            O(2)-Th(1)-O(4)             140.4(2)  
            O(8)-Th(1)-O(4)             139.0(2)  
            O(9)-Th(1)-O(4)              81.8(2)  
            O(6)-Th(1)-O(4)              86.5(3)  
            O(2)-Th(1)-O(3)              95.7(3)  
            O(8)-Th(1)-O(3)             136.0(3)  
            O(9)-Th(1)-O(3)              77.5(2)  
            O(6)-Th(1)-O(3)             136.9(2)  
            O(4)-Th(1)-O(3)              74.6(3)  
            O(2)-Th(1)-O(7)             129.6(3)  
            O(8)-Th(1)-O(7)              68.6(2)  
            O(9)-Th(1)-O(7)              69.7(2)  
            O(6)-Th(1)-O(7)              68.8(2)  
            O(4)-Th(1)-O(7)              70.5(2)  
            O(3)-Th(1)-O(7)             134.7(2)  
            O(2)-Th(1)-O(1)              66.6(2)  
            O(8)-Th(1)-O(1)              70.4(2)  
            O(9)-Th(1)-O(1)              69.6(2)  
            O(6)-Th(1)-O(1)             137.3(2)  
            O(4)-Th(1)-O(1)             135.3(3)  
            O(3)-Th(1)-O(1)              66.3(2)  
            O(7)-Th(1)-O(1)             125.4(2)  
! 190!
            O(2)-Th(1)-O(5)              69.7(2)  
            O(8)-Th(1)-O(5)             137.1(2)  
            O(9)-Th(1)-O(5)             141.3(3)  
            O(6)-Th(1)-O(5)              68.1(2)  
            O(4)-Th(1)-O(5)              71.1(2)  
            O(3)-Th(1)-O(5)              69.1(2)  
            O(7)-Th(1)-O(5)             122.8(2)  
            O(1)-Th(1)-O(5)             111.8(2)  
            C(65)-Pt(1)-C(67)            88.6(5)  
            C(65)-Pt(1)-C(66)           178.9(5)  
            C(67)-Pt(1)-C(66)            92.2(5)  
            C(65)-Pt(1)-C(59)            89.4(5)  
            C(67)-Pt(1)-C(59)           176.1(4)  
            C(66)-Pt(1)-C(59)            89.7(5)  
            S(14)-O(1)-Th(1)            122.9(4)  
            O(17)-Th(2)-O(11)           136.4(2)  
            O(17)-Th(2)-O(16)            73.9(2)  
            O(11)-Th(2)-O(16)           137.5(2)  
            O(17)-Th(2)-O(19)            74.1(2)  
            O(11)-Th(2)-O(19)            80.9(2)  
            O(16)-Th(2)-O(19)            82.5(2)  
            O(17)-Th(2)-O(12)            98.0(2)  
            O(11)-Th(2)-O(12)            76.2(2)  
            O(16)-Th(2)-O(12)           137.8(2)  
            O(19)-Th(2)-O(12)           136.2(2)  
            O(17)-Th(2)-O(14)           138.5(2)  
            O(11)-Th(2)-O(14)            82.2(2)  
            O(16)-Th(2)-O(14)            85.2(3)  
            O(19)-Th(2)-O(14)           138.8(2)  
            O(12)-Th(2)-O(14)            74.0(2)  
            O(17)-Th(2)-O(15)           129.4(2)  
            O(11)-Th(2)-O(15)            68.1(2)  
            O(16)-Th(2)-O(15)            69.4(2)  
            O(19)-Th(2)-O(15)            67.7(2)  
            O(12)-Th(2)-O(15)           132.5(2)  
            O(14)-Th(2)-O(15)            71.1(2)  
            O(17)-Th(2)-O(18)            69.6(2)  
            O(11)-Th(2)-O(18)           140.4(2)  
            O(16)-Th(2)-O(18)            68.6(2)  
            O(19)-Th(2)-O(18)           138.4(2)  
            O(12)-Th(2)-O(18)            69.8(2)  
            O(14)-Th(2)-O(18)            69.5(2)  
            O(15)-Th(2)-O(18)           123.6(2)  
            O(17)-Th(2)-O(13)            66.6(2)  
            O(11)-Th(2)-O(13)            71.6(2)  
            O(16)-Th(2)-O(13)           136.5(2)  
! 191!
            O(19)-Th(2)-O(13)            70.1(2)  
            O(12)-Th(2)-O(13)            67.4(2)  
            O(14)-Th(2)-O(13)           137.3(2)  
            O(15)-Th(2)-O(13)           124.9(2)  
            O(18)-Th(2)-O(13)           111.5(2)  
            C(68)-Pt(2)-C(202)           89.7(5)  
            C(68)-Pt(2)-C(62)            89.2(5)  
            C(202)-Pt(2)-C(62)          178.8(6)  
            C(68)-Pt(2)-C(63)           178.3(5)  
            C(202)-Pt(2)-C(63)           90.0(5)  
            C(62)-Pt(2)-C(63)            91.1(5)  
            S(7)-O(2)-Th(1)             137.1(4)  
            C(60)-Pt(3)-C(61)            90.9(5)  
            C(60)-Pt(3)-C(51)            87.6(5)  
            C(61)-Pt(3)-C(51)           178.1(5)  
            C(60)-Pt(3)-C(52)           178.6(5)  
            C(61)-Pt(3)-C(52)            89.9(5)  
            C(51)-Pt(3)-C(52)            91.6(5)  
            S(17)-O(3)-Th(1)            132.2(4)  
            C(201)-Pt(4)-C(56)          179.3(5)  
            C(201)-Pt(4)-C(55)           89.2(5)  
            C(56)-Pt(4)-C(55)            91.2(5)  
            C(201)-Pt(4)-C(64)           90.0(5)  
            C(56)-Pt(4)-C(64)            89.6(5)  
            C(55)-Pt(4)-C(64)           177.3(5)  
            S(11)-O(4)-Th(1)            138.8(4)  
            S(8)-O(5)-Th(1)             128.8(4)  
            S(18)-O(6)-Th(1)            135.5(4)  
            O(2)-S(7)-C(11)             102.3(5)  
            O(2)-S(7)-C(10)             103.1(5)  
            C(11)-S(7)-C(10)             99.2(6)  
            S(16)-O(7)-Th(1)            129.1(4)  
            O(5)-S(8)-C(301)            105.2(5)  
            O(5)-S(8)-C(501)            104.4(5)  
            C(301)-S(8)-C(501)           95.8(7)  
            S(9)-O(8)-Th(1)             129.2(4)  
            O(8)-S(9)-C(13)             102.6(5)  
            O(8)-S(9)-C(81)             103.8(5)  
            C(13)-S(9)-C(81)             98.5(6)  
            S(19)-O(9)-Th(1)            136.6(4)  
            O(15)-S(10)-C(86)           103.9(5)  
            O(15)-S(10)-C(70)           104.6(4)  
            C(86)-S(10)-C(70)            98.7(6)  
            O(4)-S(11)-C(315)           105.5(7)  
            O(4)-S(11)-C(316)           103.2(6)  
            C(315)-S(11)-C(316)          97.9(8)  
! 192!
            S(31)-O(11)-Th(2)           135.3(4)  
            O(19)-S(12)-C(319)          102.3(5)  
            O(19)-S(12)-C(305)          102.9(5)  
            C(319)-S(12)-C(305)         100.1(6)  
            S(20)-O(12)-Th(2)           134.5(4)  
            O(18)-S(13)-C(310)          105.4(6)  
            O(18)-S(13)-C(87)           104.6(6)  
            C(310)-S(13)-C(87)           97.0(6)  
            S(15)-O(13)-Th(2)           122.6(4)  
            O(1)-S(14)-C(303)           104.9(5)  
            O(1)-S(14)-C(314)           103.7(6)  
            C(303)-S(14)-C(314)          98.6(6)  
            S(99)-O(14)-Th(2)           141.3(4)  
            O(13)-S(15)-C(71)           103.8(5)  
            O(13)-S(15)-C(85)           103.7(5)  
            C(71)-S(15)-C(85)            98.5(6)  
            S(10)-O(15)-Th(2)           129.6(4)  
            O(7)-S(16)-C(80)            104.7(5)  
            O(7)-S(16)-C(12)            103.7(5)  
            C(80)-S(16)-C(12)            96.8(5)  
            S(21)-O(16)-Th(2)           133.3(4)  
            O(3)-S(17)-C(302)           104.6(5)  
            O(3)-S(17)-C(309)           103.8(5)  
            C(302)-S(17)-C(309)          98.7(7)  
            S(25)-O(17)-Th(2)           138.6(4)  
            O(6)-S(18)-C(82)            104.2(5)  
            O(6)-S(18)-C(306)           102.7(5)  
            C(82)-S(18)-C(306)           99.1(6)  
            S(13)-O(18)-Th(2)           128.8(4)  
            O(9)-S(19)-C(308)           103.9(6)  
            O(9)-S(19)-C(312)           103.7(6)  
            C(308)-S(19)-C(312)          98.9(7)  
            S(12)-O(19)-Th(2)           128.1(4)  
            O(12)-S(20)-C(304)          103.2(5)  
            O(12)-S(20)-C(307)          104.6(5)  
            C(304)-S(20)-C(307)          99.2(6)  
            O(16)-S(21)-C(90)           103.7(5)  
            O(16)-S(21)-C(89)           104.9(5)  
            C(90)-S(21)-C(89)            98.9(6)  
            O(17)-S(25)-C(84)           102.7(5)  
            O(17)-S(25)-C(88)           103.9(5)  
            C(84)-S(25)-C(88)            98.8(6)  
            O(11)-S(31)-C(311)          105.1(6)  
            O(11)-S(31)-C(313)          104.5(5)  
            C(311)-S(31)-C(313)          99.9(7)  
            N(67)-C(51)-Pt(3)           177.5(11)  
! 193!
            N(52)-C(52)-Pt(3)           176.7(12)  
            N(2)-C(55)-Pt(4)            178.5(12)  
            N(63)-C(56)-Pt(4)           178.2(12)  
            N(59)-C(59)-Pt(1)           175.6(11)  
            N(65)-C(60)-Pt(3)           178.2(12)  
            N(66)-C(61)-Pt(3)           174.8(10)  
            N(68)-C(62)-Pt(2)           178.4(13)  
            N(41)-C(63)-Pt(2)           175.9(13)  
            N(1)-C(64)-Pt(4)            176.5(15)  
            N(62)-C(65)-Pt(1)           175.6(11)  
            N(61)-C(66)-Pt(1)           177.7(13)  
            N(3)-C(67)-Pt(1)            177.7(12)  
            N(69)-C(68)-Pt(2)           177.5(12)  
            O(14)-S(99)-C(317)          105.8(6)  
            O(14)-S(99)-C(318)          103.9(6)  
            C(317)-S(99)-C(318)          97.2(8)  
            N(101)-C(201)-Pt(4)         175.6(12)  
            N(100)-C(202)-Pt(2)         177.7(13)  
           _____________________________________________________________  
   
             
 
! 194!
 
Crystallographic Table 35.  Anisotropic displacement parameters (A
2
 x 10
3
) 
for [Th(C
2
H
6
SO)
9
][Pt(CN)
4
]
2
?4H
2
O. The anisotropic displacement factor 
exponent takes the form: -2 ?
2
 [ h
2
 a*
2
 U11 + ... + 2 h k a* b* U12 ]  
   
    
_______________________________________________________________________  
   
              U11        U22        U33        U23        U13        U12  
    
_______________________________________________________________________  
   
    Th(1)    27(1)      24(1)      21(1)       4(1)       7(1)       8(1)  
    Pt(1)    37(1)      32(1)      28(1)       5(1)       8(1)       9(1)  
    O(1)     30(4)      35(4)      32(4)      10(4)      10(3)       4(3)  
    N(1)     69(9)      51(8)      86(10)     28(8)       1(7)      18(7)  
    O(1W)    77(11)    129(17)     91(14)      5(12)     10(9)     -11(10)  
    Th(2)    23(1)      23(1)      21(1)       3(1)       5(1)       7(1)  
    Pt(2)    38(1)      40(1)      36(1)       9(1)      11(1)      18(1)  
    O(2)     42(4)      42(5)      24(4)      15(4)      13(3)      18(4)  
    N(2)     67(8)      53(8)      85(10)     25(8)      20(7)       9(6)  
    O(2W)   158(19)     86(15)    150(20)     46(14)     -7(14)     32(12)  
    Pt(3)    34(1)      34(1)      26(1)       3(1)       7(1)       7(1)  
    O(3)     25(4)      35(5)      39(5)       1(4)       8(3)      -6(3)  
    N(3)     69(8)      64(9)      63(9)      33(7)       1(7)       6(6)  
    O(3W)   110(30)    170(40)    120(30)     90(30)    -10(20)     10(20)  
    Pt(4)    36(1)      39(1)      29(1)       6(1)       7(1)      14(1)  
    O(4)     36(4)      47(5)      35(5)       5(4)       6(4)       3(4)  
    O(4W)   100(30)     50(20)     80(30)     22(19)     10(20)      4(17)  
    O(5)     34(4)      52(5)      15(4)      -2(4)      15(3)      17(4)  
    O(6)     49(5)      31(4)      22(4)       0(4)      14(4)      10(4)  
    S(7)     37(2)      33(2)      22(1)       4(1)       3(1)      11(1)  
    O(7)     28(4)      31(4)      21(4)       0(3)       6(3)      10(3)  
    S(8)     30(2)      49(2)      48(2)      -5(2)       6(1)      12(1)  
    O(8)     35(4)      52(5)      17(4)       9(4)      14(3)       2(4)  
    S(9)     31(1)      36(2)      28(2)       8(1)       9(1)       4(1)  
    O(9)     47(4)      32(4)      17(4)       3(3)      15(3)      19(3)  
    S(10)    29(1)      27(2)      28(2)       2(1)       4(1)      10(1)  
    C(10)    58(8)      41(8)      23(6)     -10(6)     -21(6)      -2(6)  
    S(11)    39(2)      48(2)      28(2)      11(2)       8(1)      -3(1)  
    O(11)    29(4)      44(5)      20(4)       2(4)       9(3)      11(3)  
    C(11)    60(8)      48(8)      23(6)      15(6)      23(6)      24(6)  
    S(12)    33(1)      25(1)      32(2)       3(1)       1(1)       4(1)  
    O(12)    39(4)      27(4)      23(4)      10(3)      14(3)      11(3)  
    C(12)    44(7)      35(7)      25(6)       8(5)       8(5)      11(5)  
    S(13)    42(2)      41(2)      36(2)      14(2)      16(1)      25(1)  
! 195!
    O(13)    25(4)      35(4)      23(4)       6(3)      10(3)      12(3)  
    C(13)    39(6)      31(6)      36(7)      10(6)      11(5)      11(5)  
    S(14)    45(2)      38(2)      32(2)       4(1)       5(1)      20(1)  
    O(14)    45(4)      29(4)      20(4)      -9(3)       3(3)      11(3)  
    S(15)    31(1)      35(2)      28(2)       9(1)       7(1)      12(1)  
    O(15)    32(4)      35(4)      13(4)       5(3)      12(3)      14(3)  
    S(16)    33(1)      31(2)      27(2)       9(1)       5(1)       7(1)  
    O(16)    29(4)      43(5)      23(4)       7(4)      11(3)      16(3)  
    S(17)    35(2)      38(2)      33(2)      -5(1)      14(1)       0(1)  
    O(17)    24(4)      40(5)      33(5)       0(4)       2(3)       8(3)  
    S(18)    39(2)      29(2)      32(2)       3(1)      13(1)      10(1)  
    O(18)    38(4)      34(4)      19(4)       1(3)      19(3)      19(3)  
    S(19)    64(2)      46(2)      30(2)      13(2)      23(2)      34(2)  
    O(19)    44(4)      27(4)      28(4)       8(4)       8(3)      10(3)  
    S(20)    45(2)      25(2)      34(2)       8(1)      17(1)       8(1)  
    S(21)    37(2)      37(2)      39(2)      13(2)      21(1)      11(1)  
    S(25)    24(1)      37(2)      31(2)      10(1)       4(1)       9(1)  
    S(31)    25(1)      54(2)      35(2)      -8(2)       3(1)       8(1)  
    N(41)    48(7)      71(9)      67(9)      24(8)      -4(6)       1(6)  
    C(51)    46(7)      31(6)      24(6)     -12(5)      24(5)       2(5)  
    C(52)    52(7)      42(8)      17(6)      -4(6)      20(5)      18(6)  
    N(52)    77(9)      54(8)      49(8)      18(7)      -4(6)      -8(7)  
    C(55)    45(7)      51(8)      26(6)       8(6)      28(5)      21(6)  
    C(56)    44(7)      39(8)      48(8)      10(7)      15(6)      12(6)  
    C(59)    40(6)      37(7)      23(6)     -11(5)       5(5)      12(5)  
    N(59)    45(6)      52(7)      66(9)     -12(6)       0(6)      22(5)  
    C(60)    29(6)      50(8)      37(7)      14(6)       6(5)      10(6)  
    C(61)    37(6)      43(7)      28(6)       3(6)      24(5)       6(5)  
    N(61)    58(7)      37(7)      83(10)     12(7)      23(7)      18(6)  
    N(62)    91(9)      42(7)      38(7)      14(6)      10(6)      10(6)  
    C(62)    39(7)      51(8)      56(9)      25(7)      -4(6)      13(6)  
    N(63)    60(7)      56(7)      21(5)       5(5)       4(5)      24(6)  
    C(63)    37(7)      55(9)      35(7)      11(7)      11(6)      20(6)  
    C(64)    39(7)      70(11)     66(10)     32(9)       9(7)      32(7)  
    N(65)    44(6)      57(8)      77(9)      32(7)      13(6)       3(6)  
    C(65)    49(7)      55(9)      23(6)      26(6)      10(5)      17(6)  
    N(66)    49(6)      53(7)      36(6)      12(6)       8(5)      13(5)  
    C(66)    36(7)      48(9)      44(8)      -7(7)       4(6)      -3(6)  
    N(67)    67(8)      72(9)      41(7)      19(7)       4(6)      37(7)  
    C(67)    40(6)      38(7)      26(6)       6(6)      21(5)      10(5)  
    C(68)    49(8)      84(11)     22(7)       1(7)      17(6)      40(8)  
    N(68)    52(7)      81(9)      33(7)      -4(6)       4(5)      20(6)  
    N(69)    56(8)      56(9)     118(13)     29(9)      15(8)      19(7)  
    C(70)    50(7)      41(8)      45(8)      15(7)      15(6)      20(6)  
    C(71)    29(6)      69(9)      40(8)      15(7)      25(5)      12(6)  
    C(80)    55(8)      46(8)      22(6)       6(6)      24(6)       3(6)  
! 196!
    C(81)    40(7)      47(8)      64(9)      23(7)      31(6)      23(6)  
    C(82)    61(8)      54(8)      14(6)      -2(6)      27(5)      19(6)  
    C(84)    33(6)      35(7)      53(8)      12(6)      -5(6)       2(5)  
    C(85)    55(8)      35(7)      33(7)      -7(6)      -9(6)       4(6)  
    C(86)    53(7)      44(8)      28(7)       7(6)      -1(6)      11(6)  
    C(87)    24(6)      62(10)     85(12)      9(9)       7(7)      16(6)  
    C(88)    45(7)      49(8)      46(8)      22(7)       0(6)      14(6)  
    C(89)    75(9)      57(9)      12(6)     -10(6)      31(6)       9(7)  
    C(90)    46(7)      74(10)     37(8)       3(7)      33(6)      16(7)  
    S(99)    52(2)      35(2)      23(2)       2(1)       4(1)       2(1)  
    N(100)   64(8)      77(9)      53(8)      32(7)      12(6)      26(7)  
    N(101)   64(8)      71(9)      50(8)       9(7)     -11(6)      13(7)  
    C(201)   45(7)      38(7)      33(7)      -4(6)       4(6)      18(6)  
    C(202)   52(8)      48(9)      65(10)     15(8)      13(7)      27(7)  
    C(301)   55(8)      57(9)      42(8)      -9(7)      29(7)       9(7)  
    C(302)   42(7)      69(10)     27(7)       1(7)      16(6)      19(6)  
    C(303)   67(9)      43(8)      31(7)       0(6)      22(6)      19(6)  
    C(304)   35(6)      42(8)      59(9)       8(7)      11(6)      -5(5)  
    C(305)   45(7)      40(8)      62(9)       8(7)      10(6)      21(6)  
    C(306)   69(9)      13(6)      81(11)     13(7)      22(8)      20(6)  
    C(307)   67(9)      47(8)      45(8)      22(7)      11(7)      20(7)  
    C(308)  118(13)     38(8)      31(8)     -11(7)      15(8)      30(8)  
    C(309)   52(8)      42(8)      66(10)     15(8)       5(7)      -9(6)  
    C(310)   67(9)      33(8)      77(11)     14(8)      12(8)      26(7)  
    C(311)   57(8)      79(11)     33(8)      -8(8)      31(7)      -7(7)  
    C(312)   42(8)      77(11)     75(11)      4(9)       0(7)      33(7)  
    C(313)   50(8)      65(10)     46(8)       1(7)      24(6)      32(7)  
    C(314)  122(13)     34(8)      47(9)      23(7)      16(9)      26(8)  
    C(315)  105(13)     53(10)     98(14)     37(11)     26(11)     25(9)  
    C(316)  163(18)    132(18)     32(9)      23(11)     67(11)     70(14)  
    C(317)   50(9)     105(15)     68(12)      5(11)     -4(8)      -9(9)  
    C(318)   55(10)    139(18)     91(14)    -68(13)    -12(9)      33(10)  
    C(319)   59(8)      41(8)      24(6)       1(6)       6(6)       7(6)  
    C(501)  102(12)     90(12)     38(8)      18(8)      62(8)      58(10)  
    
_______________________________________________________________________  
 
! 197!
 
         Crystallographic Table 36.  Hydrogen coordinates ( x 10
4
) and isotropic 
         displacement parameters (A
2
 x 10
3
) for [Th(C
2
H
6
SO)
9
][Pt(CN)
4
]
2
?4H
2
O.  
   
         ________________________________________________________________  
   
                                 x                y               z            U(eq)  
         ________________________________________________________________  
   
          H(10A)       7603          7136          4189          70  
          H(10B)       7509          6591          4613          70  
          H(10C)       6796          7181          4698          70  
          H(11A)       4636          5689          3992          59  
          H(11B)       5015          6342          4563          59  
          H(11C)       5707          5741          4505          59  
          H(12A)       2609          7567           729           51  
          H(12B)       1608          6997           393           51  
          H(12C)       2808          6869           317           51  
          H(13A)       2836          5456          3169          52  
          H(13B)       1786          5614          2754          52  
          H(13C)       1826          5632          3504          52  
          H(70A)       9445           660          3612           64  
          H(70B)       9722          1225          4267          64  
          H(70C)      10441           641          4152          64  
          H(71A)      12091          2602           800          65  
          H(71B)      11574          2302            58          65  
          H(71C)      11985          1819           500          65  
          H(80A)       2019          5629          1255          60  
          H(80B)       2486          5750           631          60  
          H(80C)       1275          5858           700           60  
          H(81A)       1718          7434          3441          68  
          H(81B)       1164          6814          3675          68  
          H(81C)       1116          6779          2922          68  
          H(82A)       4804          5999           784           62  
          H(82B)       4955          5231           630           62  
          H(82C)       5934          5787          1033          62  
          H(84A)       6782           734          1054          62  
          H(84B)       7178           979           458            62  
          H(84C)       5972          1026           582           62  
          H(85A)       8987          1206           127          68  
          H(85B)      10155           984           129          68  
          H(85C)       9747          1441          -342           68  
          H(86A)      12420          2173          4179         63  
          H(86B)      12212          1546          4492         63  
          H(86C)      11486          2127          4602         63  
          H(87A)       6452          3045          2309          87  
! 198!
          H(87B)       6694          3561          1871          87  
          H(87C)       6350          3815          2555          87  
          H(88A)       7185          2839           877           68  
          H(88B)       6227          2274           466           68  
          H(88C)       7441          2231           358           68  
          H(89A)       9020          2440          4251          73  
          H(89B)       7869          2213          4425          73  
          H(89C)       8029          2822          4082          73  
          H(90A)       6077          1503          2798          76  
          H(90B)       6257          2249          3226          76  
          H(90C)       6133          1631          3561          76  
          H(30V)       9261          7289          2158          78  
          H(30W)       9160          7645          2877         78  
          H(30X)       8555          7880          2278          78  
          H(30Y)       7945          8491          3982           69  
          H(30Z)       7368          9129          4191           69  
          H(31D)       8498          9212          3945           69  
          H(30A)       5199          9352          4175           69  
          H(30B)       5128          9311          4902           69  
          H(30C)       4055          9154          4370           69  
          H(30D)      12666          4297          2245          70  
          H(30E)      12189          4692          1733           70  
          H(30F)      12415          3945          1494           70  
          H(30G)      11095           485          1387           72  
          H(30H)      10368          -235          1191          72  
          H(30I)      10808           112          1935            72  
          H(30J)       5299          4812          2262            78  
          H(30K)       6237          5087          1919           78  
          H(30L)       5269          4527          1509           78  
          H(30M)       9376          3778          1078          75  
          H(30N)      10439          3616           793          75  
          H(30O)      10261          4373          1031         75  
          H(30P)       4055          9467          2990           95  
          H(30Q)       2870          9634          2787          95  
          H(30R)       3558          9372          2245          95  
          H(30S)       6610          9660          2647           82  
          H(30T)       7717          9902          3148           82  
          H(30U)       6598          9825          3405           82  
          H(31E)       9185          4705          2794           86  
          H(31F)       7948          4784          2811           86  
          H(31G)       8324          4512          2139          86  
          H(31H)      13403          2955          2096          88  
          H(31I)      14325          2507          2215           88  
          H(31J)      13837          2884          2810          88  
          H(31K)       1274          7948          1911          98  
          H(31L)       1920          8478          1606           98  
! 199!
          H(31M)       1200          8724          2136          98  
          H(31N)      12909          1056          2738          77  
          H(31O)      13599          1733          3180          77  
          H(31P)      14023          1350          2561           77  
          H(31Q)       4251          7483          4804           97  
          H(31R)       3492          8042          4759           97  
          H(31S)       4579          8206          5279          97  
          H(31T)       5202          8881          1345          121  
          H(31U)       5639          8736           677          121  
          H(31V)       6444          8808          1340         121  
          H(31W)       6377          7027           526         149  
          H(31X)       7155          7692           926          149  
          H(31Y)       6439          7686           249          149  
          H(31Z)      12731          3774          3807         120  
          H(32A)      12566          4275          4447         120  
          H(32B)      12118          4397          3754         120  
          H(32C)       9596          4053          4354          166  
          H(32D)      10300          4553          4045         166  
          H(32E)      10722          4462          4753         166  
          H(31A)       7758            85          1799            64  
          H(31B)       8785          -150          2164           64  
          H(31C)       8351          -471          1415          64  
          H(50A)       7776          6049          2920         102  
          H(50B)       8598          6702          3303         102  
          H(50C)       8872          6244          2669         102  
         ________________________________________________________________ 
 
  
! 200!
Crystallographic Table 37 Crystal data and structure refinement for Usalzine. 
   
   
      Identification code                Usalzine 
      Empirical formula                   C
25
 H
26
 N
4
 O
7
 S
2
 U  
      Formula weight                      796.65  
      Temperature                         182(2) K 
      Wavelength                          0.71073 A 
      Crystal system, space group         Monoclinic,  P2(1)/n  
      Unit cel dimensions                a = 8.6053(18) ?   ? = 90 ? 
                                          b = 20.457(4) ?    ? = 101.532(3) ? 
                                           c = 16.111(3) ?   ? = 90 ? 
      Volume                              2778.9(10) ?
 3
 
      Z, Calculated density               4,  1.904 Mg/m
3
 
      Absorption coeficient              6.042 mm
-1
 
      F(000)                               1536  
      Crystal size                        0.17 x 0.13 x 0.10 mm 
      Theta range for data collection     1.63 to 24.75 deg.  
      Limiting indices                    -10<=h<=9, -24<=k<=24, -18<=l<=18  
      Reflections collected / unique     40617 / 4727 [R(int) = 0.0754]  
      Completenes to theta = 24.75      99.5 %  
      Absorption correction              None 
      Max. and min. transmision          0.5918 and 0.4178  
      Refinement method                   Full-matrix least-squares on F
2
 
      Data / restraints / parameters      4727 / 12 / 351  
      Goodnes-of-fit on F^2             1.105  
      Final R indices [I>2sigma(I)]      R1 = 0.0441, wR2 = 0.1111  
       R indices (al data)                R1 = 0.0590, wR2 = 0.1234  
       Largest dif. peak and hole        3.058 and -0.927 e. ?
 -3
 
   
  
! 201!
Crystallographic Table 38 Atomic coordinates ( x 10
4
) and equivalent     isotropic 
displacement parameters (?
 2
 x 10
3
) for Usalzine. U(eq) is defined as one third of the 
trace of the orthogonalized Uij tensor.  
   
         ________________________________________________________________  
   
                                x                 y                 z           U(eq)  
         ________________________________________________________________  
   
          U(1)          964(1)       2095(1)       1341(1)       26(1)  
          S(1)         -914(3)       2546(1)       -778(1)       30(1)  
          S(2)         3331(3)       9518(1)       8542(2)       46(1)  
          O(5)         1250(9)        988(3)       1909(4)       50(2)  
          O(6)          881(8)       1063(3)        533(4)       42(2)  
          N(2)          306(8)       4236(3)       2254(4)       28(2)  
          O(3)         1245(7)       2270(3)       2723(4)       32(1)  
          O(2)         3001(9)       2151(3)       1422(4)       41(2)  
          O(4)          535(6)       2467(3)        -55(3)       27(1)  
          O(7)         4764(10)      9916(4)       8485(5)       60(2)  
          C(8)         1264(9)       3841(4)       1186(5)       23(1)  
          C(3)        -1058(11)      2585(5)       4323(6)       39(2)  
          N(4)         2225(8)       5690(3)        276(4)       29(2)  
          N(3)         2990(7)       4522(3)       -519(4)       26(1)  
          C(20)        1120(11)       724(4)       1192(6)       40(2)  
          C(21)        1212(14)        -5(5)       1144(7)       53(3)  
          N(1)          846(7)       3324(3)       1623(4)       26(2)  
          C(19)         939(9)       4448(4)       1564(5)       23(1)  
          C(7)          292(10)      3576(4)       2254(5)       28(2)  
          C(6)         -263(9)       3217(4)       2937(5)       28(2)  
          C(5)        -1217(10)      3526(4)       3429(5)       33(2)  
          C(4)        -1606(11)      3214(5)       4124(6)       39(2)  
          C(2)         -151(11)      2262(5)       3845(6)       37(2)  
          C(1)          265(10)      2570(4)       3145(5)       27(2)  
          C(18)        1258(10)      5056(4)       1303(5)       29(2)  
          C(17)        1935(10)      5090(4)        569(5)       28(2)  
          C(16)        2910(10)      5707(4)       -405(5)       30(2)  
          C(15)        3243(10)      6321(4)       -753(5)       32(2)  
          C(14)        3951(11)      6350(5)      -1413(6)       39(2)  
          C(13)        4404(11)      5779(4)      -1792(6)       37(2)  
          C(12)        4089(10)      5173(4)      -1504(5)       33(2)  
          C(11)        3324(10)      5125(4)       -801(5)       28(2)  
          C(10)        2314(9)       4503(4)        160(5)       24(2)  
          C(9)         1964(10)      3882(4)        474(5)       26(2)  
          O(1)        -1084(9)       2068(3)       1242(4)       43(2)  
          C(22)        -229(14)      3124(5)      -1430(6)       52(3)  
          C(23)        -854(12)      1825(5)      -1396(6)       50(3)  
! 202!
          C(24)        3329(14)      8875(5)       7814(7)       55(3)  
          C(25)        3888(17)      9068(6)       9494(7)       74(4)  
         ________________________________________________________________  
 
! 203!
 
Crystallographic Table 39 Bond lengths [?] and angles [?] for Usalzine. 
           _____________________________________________________________  
   
            U(1)-O(2)                      1.735(8)  
            U(1)-O(1)                      1.739(8)  
            U(1)-O(3)                      2.221(6)  
            U(1)-O(4)                      2.333(5)  
            U(1)-O(5)                      2.437(6)  
            U(1)-O(6)                      2.474(6)  
            U(1)-N(1)                      2.559(7)  
            U(1)-C(20)                     2.822(9)  
            S(1)-O(4)                      1.535(6)  
            S(1)-C(22)                     1.759(10)  
            S(1)-C(23)                     1.788(10)  
            S(2)-O(7)                      1.496(8)  
            S(2)-C(24)                     1.762(11)  
            S(2)-C(25)                     1.771(11)  
            O(5)-C(20)                     1.259(12)  
            O(6)-C(20)                     1.252(11)  
            N(2)-C(7)                      1.350(10)  
            N(2)-C(19)                     1.400(11)  
            N(2)-H(2)                      0.8800  
            O(3)-C(1)                      1.334(10)  
            C(8)-N(1)                      1.358(11)  
            C(8)-C(9)                      1.402(11)  
            C(8)-C(19)                     1.435(10)  
            C(3)-C(2)                      1.370(13)  
            C(3)-C(4)                      1.386(14)  
            C(3)-H(3)                      0.9500  
            N(4)-C(16)                     1.345(11)  
            N(4)-C(17)                     1.357(10)  
            N(3)-C(10)                     1.339(10)  
            N(3)-C(11)                     1.365(10)  
            C(20)-C(21)                    1.495(13)  
            C(21)-H(21A)                   0.9800  
            C(21)-H(21B)                   0.9800  
            C(21)-H(21C)                   0.9800  
            N(1)-C(7)                      1.313(10)  
            C(19)-C(18)                    1.358(12)  
            C(7)-C(6)                      1.478(11)  
            C(6)-C(5)                      1.401(12)  
            C(6)-C(1)                      1.418(12)  
            C(5)-C(4)                      1.387(12)  
            C(5)-H(5)                      0.9500  
            C(4)-H(4)                      0.9500  
! 204!
            C(2)-C(1)                      1.400(12)  
            C(2)-H(2A)                     0.9500  
            C(18)-C(17)                    1.421(12)  
            C(18)-H(18)                    0.9500  
            C(17)-C(10)                    1.438(11)  
            C(16)-C(15)                    1.429(11)  
            C(16)-C(11)                    1.429(12)  
            C(15)-C(14)                    1.328(12)  
            C(15)-H(15)                    0.9500  
            C(14)-C(13)                    1.409(14)  
            C(14)-H(14)                    0.9500  
            C(13)-C(12)                    1.369(12)  
            C(13)-H(13)                    0.9500  
            C(12)-C(11)                    1.423(12)  
            C(12)-H(12)                    0.9500  
            C(10)-C(9)                     1.420(11)  
            C(9)-H(9)                      0.9500  
            C(22)-H(22A)                   0.9800  
            C(22)-H(22B)                   0.9800  
            C(22)-H(22C)                   0.9800  
            C(23)-H(23A)                   0.9800  
            C(23)-H(23B)                   0.9800  
            C(23)-H(23C)                   0.9800  
            C(24)-H                        0.9800  
            C(24)-HA                       0.9800  
            C(24)-HB                       0.9800  
            C(25)-HC                       0.9800  
            C(25)-HD                       0.9800  
            C(25)-HE                       0.9800  
   
            O(2)-U(1)-O(1)               177.9(3)  
            O(2)-U(1)-O(3)                90.5(2)  
            O(1)-U(1)-O(3)                90.1(3)  
            O(2)-U(1)-O(4)              90.8(2)  
            O(1)-U(1)-O(4)                87.7(2)  
            O(3)-U(1)-O(4)               151.6(2)  
            O(2)-U(1)-O(5)                90.4(3)  
            O(1)-U(1)-O(5)                91.7(3)  
            O(3)-U(1)-O(5)                77.9(2)  
            O(4)-U(1)-O(5)               130.5(2)  
            O(2)-U(1)-O(6)             91.0(2)  
            O(1)-U(1)-O(6)                90.2(2)  
            O(3)-U(1)-O(6)               130.6(2)  
            O(4)-U(1)-O(6)                77.80(19)  
            O(5)-U(1)-O(6)              52.7(2)  
            O(2)-U(1)-N(1)               89.9(2)  
! 205!
            O(1)-U(1)-N(1)                88.4(2)  
            O(3)-U(1)-N(1)                70.4(2)  
            O(4)-U(1)-N(1)                81.2(2)  
            O(5)-U(1)-N(1)               148.3(2)  
            O(6)-U(1)-N(1)               159.0(2)  
            O(2)-U(1)-C(20)               90.4(3)  
            O(1)-U(1)-C(20)               91.4(3)  
            O(3)-U(1)-C(20)              104.3(2)  
            O(4)-U(1)-C(20)              104.1(2)  
            O(5)-U(1)-C(20)               26.4(2)  
            O(6)-U(1)-C(20)               26.3(2)  
            N(1)-U(1)-C(20)              174.7(2)  
            O(4)-S(1)-C(22)              101.9(4)  
            O(4)-S(1)-C(23)              103.1(4)  
            C(22)-S(1)-C(23)              99.9(6)  
            O(7)-S(2)-C(24)              104.9(5)  
            O(7)-S(2)-C(25)              104.6(5)  
            C(24)-S(2)-C(25)              98.7(6)  
            C(20)-O(5)-U(1)               94.1(5)  
            C(20)-O(6)-U(1)               92.6(5)  
            C(7)-N(2)-C(19)              108.3(6)  
            C(7)-N(2)-H(2)               125.9  
            C(19)-N(2)-H(2)              125.9  
            C(1)-O(3)-U(1)               129.2(5)  
            S(1)-O(4)-U(1)               135.5(3)  
            N(1)-C(8)-C(9)               132.3(7)  
            N(1)-C(8)-C(19)              111.1(7)  
            C(9)-C(8)-C(19)              116.6(7)  
            C(2)-C(3)-C(4)               121.6(8)  
            C(2)-C(3)-H(3)               119.2  
            C(4)-C(3)-H(3)               119.2  
            C(16)-N(4)-C(17)             116.7(7)  
            C(10)-N(3)-C(11)             116.9(7)  
            O(6)-C(20)-O(5)              120.6(8)  
            O(6)-C(20)-C(21)             120.7(9)  
            O(5)-C(20)-C(21)             118.7(9)  
            O(6)-C(20)-U(1)               61.1(5)  
            O(5)-C(20)-U(1)               59.5(4)  
            C(21)-C(20)-U(1)             178.2(8)  
            C(20)-C(21)-H(21A)           109.5  
            C(20)-C(21)-H(21B)           109.5  
            H(21A)-C(21)-H(21B)          109.5  
            C(20)-C(21)-H(21C)           109.5  
            H(21A)-C(21)-H(21C)          109.5  
            H(21B)-C(21)-H(21C)          109.5  
            C(7)-N(1)-C(8)               105.7(7)  
! 206!
            C(7)-N(1)-U(1)               123.9(5)  
            C(8)-N(1)-U(1)               130.4(5)  
            C(18)-C(19)-N(2)             131.5(7)  
            C(18)-C(19)-C(8)             126.3(8)  
            N(2)-C(19)-C(8)              102.1(7)  
            N(1)-C(7)-N(2)               112.9(7)  
            N(1)-C(7)-C(6)               127.0(8)  
            N(2)-C(7)-C(6)               120.1(7)  
            C(5)-C(6)-C(1)               118.9(7)  
            C(5)-C(6)-C(7)               120.7(8)  
            C(1)-C(6)-C(7)               120.3(7)  
            C(4)-C(5)-C(6)               120.8(9)  
            C(4)-C(5)-H(5)               119.6  
            C(6)-C(5)-H(5)               119.6  
            C(3)-C(4)-C(5)               119.3(8)  
            C(3)-C(4)-H(4)               120.4  
            C(5)-C(4)-H(4)               120.4  
            C(3)-C(2)-C(1)               120.1(9)  
            C(3)-C(2)-H(2A)              120.0  
            C(1)-C(2)-H(2A)              120.0  
            O(3)-C(1)-C(2)               119.5(8)  
            O(3)-C(1)-C(6)               121.0(7)  
            C(2)-C(1)-C(6)               119.3(8)  
            C(19)-C(18)-C(17)            116.4(7)  
            C(19)-C(18)-H(18)            121.8  
            C(17)-C(18)-H(18)            121.8  
            N(4)-C(17)-C(18)            118.0(7)  
            N(4)-C(17)-C(10)             121.4(7)  
            C(18)-C(17)-C(10)            120.6(7)  
            N(4)-C(16)-C(15)             119.9(8)  
            N(4)-C(16)-C(11)             122.1(7)  
            C(15)-C(16)-C(11)            118.0(8)  
            C(14)-C(15)-C(16)            120.9(9)  
            C(14)-C(15)-H(15)            119.6  
            C(16)-C(15)-H(15)            119.6  
            C(15)-C(14)-C(13)            121.5(8)  
            C(15)-C(14)-H(14)            119.2  
            C(13)-C(14)-H(14)            119.2  
            C(12)-C(13)-C(14)            120.8(8)  
            C(12)-C(13)-H(13)            119.6  
            C(14)-C(13)-H(13)            119.6  
            C(13)-C(12)-C(11)            119.1(8)  
            C(13)-C(12)-H(12)            120.4  
            C(11)-C(12)-H(12)            120.4  
            N(3)-C(11)-C(12)             119.3(7)  
            N(3)-C(11)-C(16)             121.1(7)  
! 207!
            C(12)-C(11)-C(16)            119.6(8)  
            N(3)-C(10)-C(9)              118.3(7)  
            N(3)-C(10)-C(17)             121.7(7)  
            C(9)-C(10)-C(17)             120.0(7)  
            C(8)-C(9)-C(10)              120.1(7)  
            C(8)-C(9)-H(9)               119.9  
            C(10)-C(9)-H(9)              119.9  
            S(1)-C(22)-H(22A)            109.5  
            S(1)-C(22)-H(22B)            109.5  
            H(22A)-C(22)-H(22B)          109.5  
            S(1)-C(22)-H(22C)            109.5  
            H(22A)-C(22)-H(22C)          109.5  
            H(22B)-C(22)-H(22C)          109.5  
            S(1)-C(23)-H(23A)            109.5  
            S(1)-C(23)-H(23B)            109.5  
            H(23A)-C(23)-H(23B)          109.5  
            S(1)-C(23)-H(23C)            109.5  
            H(23A)-C(23)-H(23C)          109.5  
            H(23B)-C(23)-H(23C)          109.5  
            S(2)-C(24)-H                 109.5  
            S(2)-C(24)-HA                109.5  
            H-C(24)-HA                   109.5  
            S(2)-C(24)-HB                109.5  
            H-C(24)-HB                   109.5  
            HA-C(24)-HB                  109.5  
            S(2)-C(25)-HC                109.5  
            S(2)-C(25)-HD                109.5  
            HC-C(25)-HD                  109.5  
            S(2)-C(25)-HE                109.5  
            HC-C(25)-HE                  109.5  
            HD-C(25)-HE                  109.5  
           _____________________________________________________________  
   
             
 
! 208!
 
Crystallographic Table 40 Anisotropic displacement parameters (?
 2
 x 10
3
) for 
Usalzine. The anisotropic displacement factor exponent takes the form: 
-2 ?
2
 [ h
2
 a*
2
 U11 + ... + 2 h k a* b* U12 ]  
   
    
_______________________________________________________________________  
   
              U11        U22        U33        U23        U13        U12  
    
_______________________________________________________________________  
   
    U(1)     35(1)      19(1)      25(1)       1(1)       7(1)      -1(1)  
    S(1)     33(1)      25(1)      31(1)       0(1)       4(1)       1(1)  
    S(2)     49(2)      47(1)      43(1)       6(1)      14(1)       4(1)  
    O(5)     89(6)      22(3)      40(4)       8(3)      16(4)       2(3)  
    O(6)     69(5)      21(3)      35(3)      -1(3)       9(3)      -1(3)  
    N(2)     40(4)      23(3)      25(4)      -2(3)      14(3)       5(3)  
    O(3)     40(4)      28(3)      30(3)       0(2)       8(3)       3(3)  
    O(2)     74(5)      29(3)      14(3)      -2(2)      -7(3)      10(3)  
    O(4)     30(3)      25(3)      26(3)       0(2)       5(2)      -3(2)  
    O(7)     78(6)      48(4)      55(5)      16(4)      17(4)     -19(4)  
    C(8)     24(3)      21(3)      20(3)      -7(2)      -9(2)       6(2)  
    C(3)     38(5)      46(5)      35(5)       6(4)      12(4)     -12(4)  
    N(4)     34(4)      19(3)      34(4)       3(3)       6(3)      -2(3)  
    N(3)     24(4)      28(4)      24(4)       0(3)       2(3)      -2(3)  
    C(20)    49(6)      22(4)      50(6)       7(4)      16(5)      -6(4)  
    C(21)    65(7)      27(5)      65(7)       6(5)       8(6)       1(5)  
    N(1)     23(3)      29(4)      27(4)      -6(3)       6(3)      -5(3)  
    C(19)    24(3)      21(3)      20(3)      -7(2)      -9(2)       6(2)  
    C(7)     26(4)      31(5)      24(4)      -1(3)      -3(3)       2(3)  
    C(6)     24(4)      33(4)      28(4)       2(4)       9(3)       0(3)  
    C(5)     33(5)      35(5)      33(5)      -1(4)      10(4)       0(4)  
    C(4)     38(5)      45(5)      40(5)      -7(4)      20(4)      -9(4)  
    C(2)     38(5)      36(5)      36(5)       5(4)       4(4)      -9(4)  
    C(1)     28(4)      27(4)      25(4)       0(3)       1(3)      -8(3)  
    C(18)    44(5)      21(4)      23(4)      -3(3)      11(4)       1(3)  
    C(17)    34(5)      22(4)      22(4)      -1(3)      -5(3)       1(3)  
    C(16)    31(5)      27(4)      29(5)       1(3)       3(4)      -4(3)  
    C(15)    34(5)      26(4)      34(5)       6(4)      -1(4)      -8(4)  
    C(14)    44(6)      33(5)      36(5)      13(4)       3(4)      -7(4)  
    C(13)    43(5)      38(5)      34(5)       9(4)      13(4)      -9(4)  
    C(12)    31(5)      35(5)      31(5)       0(4)       5(4)      -1(4)  
    C(11)    28(5)      29(4)      26(4)       0(3)       3(3)       2(3)  
    C(10)    27(4)      22(4)      23(4)       2(3)       6(3)       2(3)  
    C(9)     39(5)      17(4)      21(4)       0(3)       6(3)       0(3)  
! 209!
    O(1)     84(5)      21(3)      23(3)       0(2)       6(3)      -2(3)  
    C(22)    68(7)      48(6)      32(5)      12(5)     -11(5)     -18(5)  
    C(23)    58(7)      33(5)      52(6)     -15(5)      -5(5)       6(5)  
    C(24)    75(8)      49(6)      44(6)       8(5)      18(5)      -6(5)  
    C(25)   114(11)     64(8)      40(6)      16(6)       8(7)     -40(8)  
    
_______________________________________________________________________  
   
  
! 210!
Crystallographic Table 41  Hydrogen coordinates ( x 10
4
) and isotropic 
         displacement parameters (?
 2
 x 10
3
) for Usalzine. 
   
         ________________________________________________________________  
   
                             x             y             z           U(eq)  
         ________________________________________________________________  
   
          H(2)          -25            4490          2624         34  
          H(3)        -1316          2373          4802         47  
          H(21A)     175          -179           871             80  
          H(21B)    1515          -185          1717          80  
          H(21C)    2006          -128           813            80  
          H(5)        -1604          3955          3285          40  
          H(4)        -2240          3429          4460          47  
          H(2A)       195            1828          3989          44  
          H(18)        1040          5438          1596          34  
          H(15)        2953          6715          -510          39  
          H(14)        4157          6764         -1634          46  
          H(13)        4935          5815         -2253          45  
          H(12)        4378          4790         -1770          39  
          H(9)         2206           3495           200           31  
          H(22A)    -102            3549         -1144          78  
          H(22B)    -999            3164         -1966           78  
          H(22C)     794            2981         -1545           78  
          H(23A)     171            1798         -1571           75  
          H(23B)   -1708           1841         -1900           75  
          H(23C)    -993            1439         -1057           75  
          H              3117           9050          7237           83  
          HA           2503           8558          7874           83  
          HB           4365           8658          7929           83  
          HC           4889           8840          9493         111  
          HD           3060          8748          9537         111  
          HE           4024          9367          9978          111  
         ________________________________________________________________  
 
! 211!
 
         Crystallographic Table 42 Torsion angles [?] for Usalzine 
         ________________________________________________________________  
   
          O(2)-U(1)-O(5)-C(20)                                -90.0(6)  
          O(1)-U(1)-O(5)-C(20)                                 89.8(6)  
          O(3)-U(1)-O(5)-C(20)                                179.6(6)  
          O(4)-U(1)-O(5)-C(20)                                  1.4(7)  
          O(6)-U(1)-O(5)-C(20)                                  0.9(5)  
          N(1)-U(1)-O(5)-C(20)                                179.5(5)  
          O(2)-U(1)-O(6)-C(20)                                 88.9(6)  
          O(1)-U(1)-O(6)-C(20)                                -92.9(6)  
          O(3)-U(1)-O(6)-C(20)                                 -2.6(7)  
          O(4)-U(1)-O(6)-C(20)                                179.5(6)  
          O(5)-U(1)-O(6)-C(20)                                 -0.9(5)  
          N(1)-U(1)-O(6)-C(20)                               -178.9(6)  
          O(2)-U(1)-O(3)-C(1)                                 148.1(6)  
          O(1)-U(1)-O(3)-C(1)                                 -29.9(6)  
          O(4)-U(1)-O(3)-C(1)                                  55.5(8)  
          O(5)-U(1)-O(3)-C(1)                                -121.6(7)  
          O(6)-U(1)-O(3)-C(1)                                -120.2(6)  
          N(1)-U(1)-O(3)-C(1)                                  58.4(6)  
          C(20)-U(1)-O(3)-C(1)                               -121.4(6)  
          C(22)-S(1)-O(4)-U(1)                                159.2(6)  
          C(23)-S(1)-O(4)-U(1)                                -97.6(6)  
          O(2)-U(1)-O(4)-S(1)                                 173.2(5)  
          O(1)-U(1)-O(4)-S(1)                                  -8.4(5)  
          O(3)-U(1)-O(4)-S(1)                                 -94.4(6)  
          O(5)-U(1)-O(4)-S(1)                                  81.9(5)  
          O(6)-U(1)-O(4)-S(1)                                  82.3(5)  
          N(1)-U(1)-O(4)-S(1)                                 -97.1(5)  
          C(20)-U(1)-O(4)-S(1)                                 82.5(5)  
          U(1)-O(6)-C(20)-O(5)                                  1.7(10)  
          U(1)-O(6)-C(20)-C(21)                              -180.0(8)  
          U(1)-O(5)-C(20)-O(6)                                 -1.7(10)  
          U(1)-O(5)-C(20)-C(21)                               179.9(8)  
          O(2)-U(1)-C(20)-O(6)                                -91.5(6)  
          O(1)-U(1)-C(20)-O(6)                                 87.5(6)  
          O(3)-U(1)-C(20)-O(6)                                177.9(5)  
          O(4)-U(1)-C(20)-O(6)                                 -0.5(6)  
          O(5)-U(1)-C(20)-O(6)                                178.3(10)  
          N(1)-U(1)-C(20)-O(6)                                176(2)  
          O(2)-U(1)-C(20)-O(5)                                 90.2(6)  
          O(1)-U(1)-C(20)-O(5)                                -90.9(6)  
          O(3)-U(1)-C(20)-O(5)                                 -0.4(6)  
          O(4)-U(1)-C(20)-O(5)                               -178.9(6)  
! 212!
          O(6)-U(1)-C(20)-O(5)                               -178.3(10)  
          N(1)-U(1)-C(20)-O(5)                                 -3(3)  
          O(2)-U(1)-C(20)-C(21)                                88(22)  
          O(1)-U(1)-C(20)-C(21)                               -93(22)  
          O(3)-U(1)-C(20)-C(21)                                -3(22)  
          O(4)-U(1)-C(20)-C(21)                               179(100)  
          O(5)-U(1)-C(20)-C(21)                                -2(22)  
          O(6)-U(1)-C(20)-C(21)                               179(100)  
          N(1)-U(1)-C(20)-C(21)                                -5(24)  
          C(9)-C(8)-N(1)-C(7)                                 177.7(8)  
          C(19)-C(8)-N(1)-C(7)                                 -0.4(8)  
          C(9)-C(8)-N(1)-U(1)                                  -3.9(12)  
          C(19)-C(8)-N(1)-U(1)                                178.0(5)  
          O(2)-U(1)-N(1)-C(7)                                -121.6(6)  
          O(1)-U(1)-N(1)-C(7)                                  59.6(6)  
          O(3)-U(1)-N(1)-C(7)                                 -31.1(6)  
          O(4)-U(1)-N(1)-C(7)                                 147.5(6)  
          O(5)-U(1)-N(1)-C(7)                                 -31.0(8)  
          O(6)-U(1)-N(1)-C(7)                                 145.9(7)  
          C(20)-U(1)-N(1)-C(7)                                -29(3)  
          O(2)-U(1)-N(1)-C(8)                                  60.2(6)  
          O(1)-U(1)-N(1)-C(8)                                -118.6(7)  
          O(3)-U(1)-N(1)-C(8)                                 150.7(7)  
          O(4)-U(1)-N(1)-C(8)                                 -30.6(6)  
          O(5)-U(1)-N(1)-C(8)                                 150.8(6)  
          O(6)-U(1)-N(1)-C(8)                                 -32.3(10)  
          C(20)-U(1)-N(1)-C(8)                                153(2)  
          C(7)-N(2)-C(19)-C(18)                              -177.3(8)  
          C(7)-N(2)-C(19)-C(8)                                  0.2(8)  
          N(1)-C(8)-C(19)-C(18)                               177.8(7)  
          C(9)-C(8)-C(19)-C(18)                                -0.6(11)  
          N(1)-C(8)-C(19)-N(2)                                  0.1(8)  
          C(9)-C(8)-C(19)-N(2)                               -178.3(6)  
          C(8)-N(1)-C(7)-N(2)                                   0.6(9)  
          U(1)-N(1)-C(7)-N(2)                                -178.0(5)  
          C(8)-N(1)-C(7)-C(6)                                -177.4(7)  
          U(1)-N(1)-C(7)-C(6)                                   4.0(11)  
          C(19)-N(2)-C(7)-N(1)                                 -0.5(9)  
          C(19)-N(2)-C(7)-C(6)                                177.6(7)  
          N(1)-C(7)-C(6)-C(5)                                -162.2(8)  
          N(2)-C(7)-C(6)-C(5)                                  19.9(12)  
          N(1)-C(7)-C(6)-C(1)                                  22.7(12)  
          N(2)-C(7)-C(6)-C(1)                                -155.2(8)  
          C(1)-C(6)-C(5)-C(4)                                   1.9(13)  
          C(7)-C(6)-C(5)-C(4)                                -173.3(8)  
          C(2)-C(3)-C(4)-C(5)                                  -0.5(14)  
! 213!
          C(6)-C(5)-C(4)-C(3)                                  -1.0(13)  
          C(4)-C(3)-C(2)-C(1)                                   1.1(14)  
          U(1)-O(3)-C(1)-C(2)                                 129.6(7)  
          U(1)-O(3)-C(1)-C(6)                                 -55.2(10)  
          C(3)-C(2)-C(1)-O(3)                                 175.0(8)  
          C(3)-C(2)-C(1)-C(6)                                  -0.2(13)  
          C(5)-C(6)-C(1)-O(3)                                -176.4(8)  
          C(7)-C(6)-C(1)-O(3)                                  -1.2(12)  
          C(5)-C(6)-C(1)-C(2)                                  -1.3(12)  
          C(7)-C(6)-C(1)-C(2)                                 173.9(8)  
          N(2)-C(19)-C(18)-C(17)                              179.0(8)  
          C(8)-C(19)-C(18)-C(17)                                2.0(12)  
          C(16)-N(4)-C(17)-C(18)                              178.1(7)  
          C(16)-N(4)-C(17)-C(10)                               -1.3(11)  
          C(19)-C(18)-C(17)-N(4)                              178.0(7)  
          C(19)-C(18)-C(17)-C(10)                              -2.6(12)  
          C(17)-N(4)-C(16)-C(15)                              179.6(7)  
          C(17)-N(4)-C(16)-C(11)                               -0.3(12)  
          N(4)-C(16)-C(15)-C(14)                              178.5(8)  
          C(11)-C(16)-C(15)-C(14)                              -1.6(12)  
          C(16)-C(15)-C(14)-C(13)                              -0.2(13)  
          C(15)-C(14)-C(13)-C(12)                               1.7(14)  
          C(14)-C(13)-C(12)-C(11)                              -1.4(13)  
          C(10)-N(3)-C(11)-C(12)                              178.0(7)  
          C(10)-N(3)-C(11)-C(16)                               -2.4(11)  
          C(13)-C(12)-C(11)-N(3)                              179.1(8)  
          C(13)-C(12)-C(11)-C(16)                              -0.5(12)  
          N(4)-C(16)-C(11)-N(3)                                 2.2(12)  
          C(15)-C(16)-C(11)-N(3)                             -177.7(7)  
          N(4)-C(16)-C(11)-C(12)                             -178.2(8)  
          C(15)-C(16)-C(11)-C(12)                               1.9(12)  
          C(11)-N(3)-C(10)-C(9)                              -179.4(7)  
          C(11)-N(3)-C(10)-C(17)                                0.8(11)  
          N(4)-C(17)-C(10)-N(3)                                 1.1(12)  
          C(18)-C(17)-C(10)-N(3)                             -178.3(7)  
          N(4)-C(17)-C(10)-C(9)                              -178.7(7)  
          C(18)-C(17)-C(10)-C(9)                                2.0(12)  
          N(1)-C(8)-C(9)-C(10)                               -178.2(8)  
          C(19)-C(8)-C(9)-C(10)                                -0.1(11)  
          N(3)-C(10)-C(9)-C(8)                                179.7(7)  
          C(17)-C(10)-C(9)-C(8)                                -0.6(12)  
         ________________________________________________________________  
   
  
! 214!
Crystallographic Table 43 Crystal data and structure refinement for salzine.  
   
   
        Identification code            salzine 
        Empirical formula                  C
19
 H
12
 N
4
 O  
        Formula weight                     312.33  
        Temperature                        296(2) K 
        Wavelength                         0.71073 A 
        Crystal system, space group        Monoclinic,  P2
1
/n 
        Unit cel dimensions               a = 6.692(3) ?    alpha = 90 ? 
                                        b = 26.911(14) ?     beta = 104.413(9) ? 
                                         c = 8.086(4) ?    gama = 90 ? 
        Volume                             1410.3(12) ?
 3
 
        Z, Calculated density              4,  1.471 Mg/m
3
 
        Absorption coeficient            0.096 mm
-1
 
        F(000)                             648  
        Crystal size                       0.1 x 0.1 x 0.1 mm 
        Theta range for data collection    2.71 to 26.47 deg.  
        Limiting indices                   -8<=h<=8, -33<=k<=33, -10<=l<=10  
        Reflections collected / unique     13099 / 2924 [R(int) = 0.0581]  
        Completenes to theta = 26.47     99.8 %  
        Refinement method                  Full-matrix least-squares on F
2
 
        Data / restraints / parameters     2924 / 0 / 220  
        Goodness-of-fit on F^2             1.032  
        Final R indices [I>2sigma(I)]      R1 = 0.0428, wR2 = 0.0895  
        R indices (al data)               R1 = 0.0700, wR2 = 0.1013  
        Largest dif. peak and hole        0.189 and -0.199 e. ?
 -3
 
! 215!
 
Crystallographic Table 4 Salzine Atomic coordinates ( x 10
4
) and equivalent 
isotropic displacement parameters (A
2
 x 10
3
) for salzine. U(eq) is defined as one 
third of the trace of the orthogonalized Uij tensor.  
   
         ________________________________________________________________  
   
                               x                 y                    z           U(eq)  
         ________________________________________________________________  
   
          O(1)          -62(2)      10442(1)       6163(2)       27(1)  
          N(1)        10015(2)       8799(1)      10557(2)       24(1)  
          N(2)         6342(2)      10188(1)       7286(2)       23(1)  
          N(3)         6069(2)       8472(1)      10852(2)       22(1)  
          N(4)         3228(2)       9937(1)       7518(2)       22(1)  
          C(1)        11363(3)       7668(1)      13040(2)       32(1)  
          C(2)        11565(3)       8089(1)      12166(2)       30(1)  
          C(3)         9789(3)       8380(1)      11399(2)       23(1)  
          C(4)         8290(2)       9061(1)       9855(2)       21(1)  
          C(5)         8478(3)       9502(1)       8948(2)       22(1)  
          C(6)         6705(2)       9756(1)       8239(2)       20(1)  
          C(7)         4265(2)      10279(1)       6889(2)       21(1)  
          C(8)         3293(3)      10703(1)       5882(2)       21(1)  
          C(9)         4441(3)      11055(1)       5243(2)       27(1)  
          C(10)        3513(3)      11451(1)       4280(2)       31(1)  
          C(11)        1379(3)      11501(1)       3917(2)       30(1)  
          C(12)        9389(3)       7504(1)      13192(2)       31(1)  
          C(13)        7665(3)       7770(1)      12468(2)       28(1)  
          C(14)        7801(3)       8215(1)      11555(2)       22(1)  
          C(15)        6274(3)       8894(1)      10003(2)       20(1)  
          C(16)        4477(2)       9171(1)       9249(2)       21(1)  
          C(17)        4699(2)       9595(1)       8380(2)       20(1)  
          C(18)        1135(3)      10763(1)       5535(2)       22(1)  
          C(19)         198(3)      11160(1)       4532(2)       27(1)  
         ________________________________________________________________  
 
! 216!
 
           Crystallographic Table 45 Bond lengths [?] and angles [?] for salzine.  
           _____________________________________________________________  
   
            O(1)-C(18)                     1.360(2)  
            O(1)-H(9)                      0.98(2)  
            N(1)-C(3)                      1.345(2)  
            N(1)-C(4)                      1.351(2)  
            N(2)-C(7)                      1.369(2)  
            N(2)-C(6)                      1.383(2)  
            N(2)-H(3)                      0.8600  
            N(3)-C(14)                     1.347(2)  
            N(3)-C(15)                     1.353(2)  
            N(4)-C(7)                      1.328(2)  
            N(4)-C(17)                     1.399(2)  
            C(1)-C(2)                      1.360(3)  
            C(1)-C(12)                     1.427(3)  
            C(1)-H(1)                      0.9300  
            C(2)-C(3)                      1.428(2)  
            C(2)-H(7)                      0.9300  
            C(3)-C(14)                     1.438(2)  
            C(4)-C(5)                      1.417(2)  
            C(4)-C(15)                     1.454(2)  
            C(5)-C(6)                      1.366(2)  
            C(5)-H(8)                      0.9300  
            C(6)-C(17)                     1.442(2)  
            C(7)-C(8)                      1.457(2)  
            C(8)-C(9)                      1.398(2)  
            C(8)-C(18)                     1.410(2)  
            C(9)-C(10)                     1.375(2)  
            C(9)-H(11)                     0.9300  
            C(10)-C(11)                    1.390(3)  
            C(10)-H(12)                    0.9300  
            C(11)-C(19)                    1.381(3)  
            C(11)-H(2)                     0.9300  
            C(12)-C(13)                    1.360(3)  
            C(12)-H(4)                     0.9300  
            C(13)-C(14)                    1.422(2)  
            C(13)-H(5)                     0.9300  
            C(15)-C(16)                    1.417(2)  
            C(16)-C(17)                    1.368(2)  
            C(16)-H(6)                     0.9300  
            C(18)-C(19)                    1.393(2)  
            C(19)-H(10)                    0.9300  
 
            C(18)-O(1)-H(9)              106.7(12)  
! 217!
            C(3)-N(1)-C(4)               117.26(15)  
            C(7)-N(2)-C(6)               108.00(13)  
            C(7)-N(2)-H(3)               126.0  
            C(6)-N(2)-H(3)               126.0  
            C(14)-N(3)-C(15)             117.35(15)  
            C(7)-N(4)-C(17)              106.06(14)  
            C(2)-C(1)-C(12)              121.10(17)  
            C(2)-C(1)-H(1)               119.5  
            C(12)-C(1)-H(1)              119.5  
            C(1)-C(2)-C(3)               120.15(17)  
            C(1)-C(2)-H(7)               119.9  
            C(3)-C(2)-H(7)               119.9  
            N(1)-C(3)-C(2)               119.51(16)  
            N(1)-C(3)-C(14)              121.75(15)  
            C(2)-C(3)-C(14)              118.74(16)  
            N(1)-C(4)-C(5)               118.53(15)  
            N(1)-C(4)-C(15)              121.19(15)  
            C(5)-C(4)-C(15)              120.28(15)  
            C(6)-C(5)-C(4)               117.18(15)  
            C(6)-C(5)-H(8)               121.4  
            C(4)-C(5)-H(8)               121.4  
            C(5)-C(6)-N(2)               131.98(15)  
            C(5)-C(6)-C(17)              123.10(15)  
            N(2)-C(6)-C(17)              104.92(14)  
            N(4)-C(7)-N(2)               112.50(14)  
            N(4)-C(7)-C(8)               123.61(15)  
            N(2)-C(7)-C(8)               123.89(14)  
            C(9)-C(8)-C(18)              118.55(16)  
            C(9)-C(8)-C(7)               121.83(16)  
            C(18)-C(8)-C(7)              119.63(14)  
            C(10)-C(9)-C(8)              121.54(17)  
            C(10)-C(9)-H(11)             119.2  
            C(8)-C(9)-H(11)              119.2  
            C(9)-C(10)-C(11)             119.32(17)  
            C(9)-C(10)-H(12)             120.3  
            C(11)-C(10)-H(12)            120.3  
            C(19)-C(11)-C(10)            120.65(17)  
            C(19)-C(11)-H(2)             119.7  
            C(10)-C(11)-H(2)             119.7  
            C(13)-C(12)-C(1)             120.32(17)  
            C(13)-C(12)-H(4)             119.8  
            C(1)-C(12)-H(4)              119.8  
            C(12)-C(13)-C(14)            120.63(17)  
            C(12)-C(13)-H(5)             119.7  
            C(14)-C(13)-H(5)             119.7  
            N(3)-C(14)-C(13)             119.44(16)  
! 218!
            N(3)-C(14)-C(3)              121.50(15)  
            C(13)-C(14)-C(3)             119.06(15)  
            N(3)-C(15)-C(16)             118.52(15)  
            N(3)-C(15)-C(4)              120.94(15)  
            C(16)-C(15)-C(4)             120.54(15)  
            C(17)-C(16)-C(15)            118.07(15)  
            C(17)-C(16)-H(6)             121.0  
            C(15)-C(16)-H(6)             121.0  
            C(16)-C(17)-N(4)             130.66(15)  
            C(16)-C(17)-C(6)             120.83(15)  
            N(4)-C(17)-C(6)              108.51(14)  
            O(1)-C(18)-C(19)             118.96(16)  
            O(1)-C(18)-C(8)              121.40(15)  
            C(19)-C(18)-C(8)             119.64(15)  
            C(11)-C(19)-C(18)            120.27(17)  
            C(11)-C(19)-H(10)            119.9  
            C(18)-C(19)-H(10)            119.9  
           _____________________________________________________________  
   
            
             
 
! 219!
 
Crystallographic Table 46 Anisotropic displacement parameters (?
 2
 x 10
3
) for 
salzine. The anisotropic displacement factor exponent takes the form: 
-2 ?^2 [ h^2 a*^2 U11 + ... + 2 h k a* b* U12 ]  
   
    
_______________________________________________________________________  
   
              U11        U22        U33        U23        U13        U12  
    
_______________________________________________________________________  
   
    O(1)     20(1)      28(1)      33(1)       4(1)       8(1)       1(1)  
    N(1)     21(1)      24(1)      28(1)      -1(1)       6(1)       1(1)  
    N(2)     19(1)      22(1)      28(1)       3(1)       8(1)      -1(1)  
    N(3)     23(1)      20(1)      24(1)      -2(1)       5(1)       0(1)  
    N(4)     20(1)      22(1)      23(1)       2(1)       4(1)       0(1)  
    C(1)     31(1)      30(1)      35(1)       5(1)       6(1)      10(1)  
    C(2)     24(1)      31(1)      35(1)       1(1)       8(1)       4(1)  
    C(3)     25(1)      21(1)      22(1)      -2(1)       6(1)       1(1)  
    C(4)     19(1)      21(1)      22(1)      -3(1)       5(1)       1(1)  
    C(5)     17(1)      23(1)      26(1)      -2(1)       8(1)      -2(1)  
    C(6)     22(1)      19(1)      21(1)      -2(1)       7(1)      -1(1)  
    C(7)     20(1)      21(1)      21(1)      -3(1)       6(1)       0(1)  
    C(8)     25(1)      20(1)      20(1)      -3(1)       6(1)       0(1)  
    C(9)     26(1)      27(1)      30(1)       1(1)       9(1)      -1(1)  
    C(10)    36(1)      26(1)      33(1)       5(1)      14(1)      -3(1)  
    C(11)    39(1)      26(1)      27(1)       5(1)       9(1)       7(1)  
    C(12)    38(1)      23(1)      34(1)       5(1)       9(1)       3(1)  
    C(13)    28(1)      23(1)      32(1)       1(1)       8(1)      -1(1)  
    C(14)    23(1)      21(1)      21(1)      -3(1)       4(1)       1(1)  
    C(15)    22(1)      19(1)      19(1)      -4(1)       6(1)      -1(1)  
    C(16)    15(1)      24(1)      24(1)      -1(1)       5(1)      -3(1)  
    C(17)    20(1)      20(1)      20(1)      -3(1)       5(1)      -1(1)  
    C(18)    25(1)      22(1)      21(1)      -4(1)       9(1)      -2(1)  
    C(19)    25(1)      29(1)      27(1)       0(1)       6(1)       7(1)  
    
_______________________________________________________________________  
 
! 220!
 
         Crystallographic Table 47 Hydrogen coordinates ( x 10
4
) and isotropic 
         displacement parameters (?
 2
 x 10
3
) for salzine.  
   
         ________________________________________________________________  
   
                                  x             y                   z           U(eq)  
         ________________________________________________________________  
   
          H(9)          860(30)     10182(7)       6780(20)      40  
          H(3)          7260         10368            6995            27  
          H(1)        12531           7484           13548            39  
          H(7)        12861           8188           12067            36  
          H(8)         9755           9613            8840             26  
          H(11)        5867         11020            5475             33  
          H(12)        4303         11684            3876             37  
          H(2)            742         11766            3253             37  
          H(4)          9281           7214          13790             38  
          H(5)          6384           7659          12570             33  
          H(6)         3184          9067            9343             25  
          H(10)       -1228         11197           4275             33  
         ________________________________________________________________  
 
! 221!
 
         Crystallographic Table 48 Salzine Torsion angles [?] for salzine.  
         ________________________________________________________________  
   
          C(12)-C(1)-C(2)-C(3)                   0.9(3)  
          C(4)-N(1)-C(3)-C(2)                    -179.99(15)  
          C(4)-N(1)-C(3)-C(14)                    -0.1(2)  
          C(1)-C(2)-C(3)-N(1)                    179.15(16)  
          C(1)-C(2)-C(3)-C(14)                   -0.7(2)  
          C(3)-N(1)-C(4)-C(5)                   -179.51(14)  
          C(3)-N(1)-C(4)-C(15)                    -0.2(2)  
          N(1)-C(4)-C(5)-C(6)                       179.41(15)  
          C(15)-C(4)-C(5)-C(6)        0.1(2)  
          C(4)-C(5)-C(6)-N(2)      -179.63(16)  
          C(4)-C(5)-C(6)-C(17)           0.1(2)  
          C(7)-N(2)-C(6)-C(5)           179.80(17)  
          C(7)-N(2)-C(6)-C(17)         0.03(17)  
          C(17)-N(4)-C(7)-N(2)     -0.31(18)  
          C(17)-N(4)-C(7)-C(8)   179.50(14)  
          C(6)-N(2)-C(7)-N(4)      0.18(18)  
          C(6)-N(2)-C(7)-C(8)   -179.63(15)  
          N(4)-C(7)-C(8)-C(9)    179.96(16)  
          N(2)-C(7)-C(8)-C(9)  -0.3(2)  
          N(4)-C(7)-C(8)-C(18)     0.0(2)  
          N(2)-C(7)-C(8)-C(18)  179.80(15)  
          C(18)-C(8)-C(9)-C(10)   -0.7(2)  
          C(7)-C(8)-C(9)-C(10)   179.36(16)  
          C(8)-C(9)-C(10)-C(11)  -0.7(3)  
          C(9)-C(10)-C(11)-C(19)    0.9(3)  
          C(2)-C(1)-C(12)-C(13)   -0.4(3)  
          C(1)-C(12)-C(13)-C(14)   -0.3(3)  
          C(15)-N(3)-C(14)-C(13)  179.70(14)  
          C(15)-N(3)-C(14)-C(3)   -0.6(2)  
          C(12)-C(13)-C(14)-N(3)   -179.91(16)  
          C(12)-C(13)-C(14)-C(3)  0.4(2)  
          N(1)-C(3)-C(14)-N(3)   0.5(2)  
          C(2)-C(3)-C(14)-N(3)     -179.61(15)  
          N(1)-C(3)-C(14)-C(13)  -179.77(15)  
          C(2)-C(3)-C(14)-C(13)    0.1(2)  
          C(14)-N(3)-C(15)-C(16)  179.96(14)  
          C(14)-N(3)-C(15)-C(4)  0.3(2)  
          N(1)-C(4)-C(15)-N(3)  0.1(2)  
          C(5)-C(4)-C(15)-N(3)   179.41(14)  
          N(1)-C(4)-C(15)-C(16)   -179.57(15)  
          C(5)-C(4)-C(15)-C(16)     -0.2(2)  
          N(3)-C(15)-C(16)-C(17)  -179.42(14)  
! 222!
          C(4)-C(15)-C(16)-C(17)   0.2(2)  
          C(15)-C(16)-C(17)-N(4)      179.82(15)  
          C(15)-C(16)-C(17)-C(6)   -0.1(2)  
          C(7)-N(4)-C(17)-C(16)  -179.57(17)  
          C(7)-N(4)-C(17)-C(6)   0.32(17)  
          C(5)-C(6)-C(17)-C(16)   -0.1(2)  
          N(2)-C(6)-C(17)-C(16)  179.69(15)  
          C(5)-C(6)-C(17)-N(4)  179.99(15)  
          N(2)-C(6)-C(17)-N(4)  -0.22(17)  
          C(9)-C(8)-C(18)-O(1)   -178.03(15)  
          C(7)-C(8)-C(18)-O(1)  1.9(2)  
          C(9)-C(8)-C(18)-C(19)  1.9(2)  
          C(7)-C(8)-C(18)-C(19)  -178.16(15)  
          C(10)-C(11)-C(19)-C(18)  0.4(3)  
          O(1)-C(18)-C(19)-C(11)  178.18(15)  
          C(8)-C(18)-C(19)-C(11)      -1.7(2)  
         ________________________________________________________________  
   
 
           
  
! 223!
 
      Crystallographic Table 49 Crystal data and structure refinement for t-butsalzine.  
   
   
        Identification code               bam137_0m 
        Empirical formula            C
32
 H
38
 N
4
 O
2
 
        Formula weight                   510.66  
        Temperature                  183(2) K 
        Wavelength                       0.71073 A 
        Crystal system, space group        Triclinic,  P-1  
        Unit cel dimensions              a = 9.0785(5) ?    ? = 103.4900(10) ? 
                                         b = 9.9896(6) ?     ? = 103.2300(10) ? 
                                         c = 16.3768(9) ?    ? = 99.4810(10) ? 
        Volume                             1368.08(13) ?
 3
 
        Z, Calculated density              2,  1.240 Mg/m
3
 
        Absorption coeficient             0.078 mm
-1
 
        F(000)                             548  
        Crystal size                       0.1 x 0.1 x 0.1 mm 
        Theta range for data collection    1.33 to 30.75 ? 
        Limiting indices                   -13<=h<=13, -14<=k<=14, -23<=l<=23  
        Reflections collected / unique     37120 / 8315 [R(
int
) = 0.0313]  
        Completenes to theta = 30.75     97.5 %  
        Absorption correction              Numerical 
        Refinement method                  Full-matrix least-squares on F
2
 
        Data / restraints / parameters     8315 / 3 / 358  
        Goodnes-of-fit on F
2
             1.646  
        Final R indices [I>2sigma(I)]      R1 = 0.0576, wR2 = 0.2008  
        R indices (al data)               R1 = 0.0659, wR2 = 0.2135  
        Largest dif. peak and hole        0.716 and -0.386 e.A
-3
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
! 224!
Crystallographic Table 50  Atomic coordinates ( x 10
4
) and 
equivalent isotropic displacement parameters (?
 2
 x 10
3
) for t-
butsalzine. U(eq) is defined as one third of the trace of the 
orthogonalized Uij tensor.  
   
         ________________________________________________________________  
   
                         x             y             z           U(eq)  
         ________________________________________________________________  
   
          O(1)        -1590(1)       6661(1)       7088(1)       31(1)  
          O(2)         7143(1)       7150(1)       4385(1)       34(1)  
          O(3)         3166(2)       9372(1)       8977(1)       58(1)  
          N(2)          365(1)       6953(1)       6203(1)       23(1)  
          N(3)         1721(1)       5305(1)       5876(1)       21(1)  
          N(4)         4074(1)       7677(1)       4043(1)       22(1)  
          C(1)         2863(3)       7116(2)       9179(2)       67(1)  
          C(2)         3054(3)       8179(2)      10042(1)       56(1)  
          C(3)         2838(3)       9496(2)       9790(2)       63(1)  
          C(4)         2694(5)       7954(2)       8529(2)      107(1)  
          C(5)          -82(2)       1332(2)       8466(1)       36(1)  
          C(6)          848(1)       2095(1)       7972(1)       23(1)  
          C(7)          130(1)       3262(1)       7692(1)       21(1)  
          C(8)          653(1)       3906(1)       7112(1)       21(1)  
          C(9)           91(1)       5045(1)       6900(1)       20(1)  
          C(10)         707(1)       5752(1)       6324(1)       20(1)  
          C(11)        1215(1)       7336(1)       5658(1)       20(1)  
          C(12)        1318(1)       8500(1)       5347(1)       22(1)  
          C(13)        2312(1)       8644(1)       4805(1)       20(1)  
          N(1)         2472(1)       9808(1)       4521(1)       22(1)  
          C(15)        3358(1)       9885(1)       3972(1)       22(1)  
          C(16)        3505(2)      11064(1)       3620(1)       28(1)  
          C(17)        4347(2)      11124(1)       3037(1)       32(1)  
          C(18)         943(2)        980(1)       7175(1)       28(1)  
          C(19)        -991(1)       3798(1)       8051(1)       22(1)  
          C(20)       -1592(1)       4927(1)       7868(1)       22(1)  
          C(21)       -2788(1)       5489(1)       8301(1)       26(1)  
          C(22)       -4314(2)       5333(2)       7602(1)       31(1)  
          C(23)       -3187(2)       4669(2)       8937(1)       34(1)  
          C(24)       -2134(2)       7055(2)       8828(1)       38(1)  
          C(25)       -1037(1)       5557(1)       7280(1)       22(1)  
          C(26)        2085(1)       6286(1)       5442(1)       19(1)  
          C(27)        3031(1)       6366(1)       4905(1)       20(1)  
          C(28)        3155(1)       7562(1)       4573(1)       19(1)  
          C(29)        4148(1)       8796(1)       3716(1)       21(1)  
          C(30)        5118(2)      10037(2)       2775(1)       32(1)  
! 225!
          C(31)        5030(2)       8910(1)       3115(1)       29(1)  
          C(32)        2510(2)       2777(2)       8572(1)       34(1)  
         ________________________________________________________________  
 
 
  
            
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
! 226!
 
Crystallographic Table 51 Bond lengths [?] and angles [?] for t-butsalzine.  
           _____________________________________________________________  
   
            O(1)-C(25)                    1.3554(13)  
            O(1)-H(20)                    0.97(2)  
            O(2)-H(37)                    0.829(9)  
            O(2)-H(38)                    0.835(9)  
            O(3)-C(4)                     1.378(3)  
            O(3)-C(3)                     1.412(3)  
            N(2)-C(10)                    1.3344(13)  
            N(2)-C(11)                    1.3846(15)  
            N(3)-C(10)                    1.3700(14)  
            N(3)-C(26)                    1.3787(13)  
            N(3)-H(21)                    0.8600  
            N(4)-C(28)                    1.3454(15)  
            N(4)-C(29)                    1.3450(14)  
            C(1)-C(4)                     1.496(3)  
            C(1)-C(2)                     1.510(3)  
            C(1)-H(1)                     0.9700  
            C(1)-H(4)                     0.9700  
            C(2)-C(3)                     1.497(3)  
            C(2)-H(6)                     0.9700  
            C(2)-H(5)                     0.9700  
            C(3)-H(2)                     0.9700  
            C(3)-H(7)                     0.9700  
            C(5)-C(6)                     1.5283(17)  
            C(5)-H(31)                    0.9600  
            C(5)-H(8)                     0.9600  
            C(5)-H(30)                    0.9600  
            C(6)-C(7)                     1.5357(15)  
            C(6)-C(18)                    1.5358(17) 
            C(6)-C(32)                    1.5408(18)  
            C(7)-C(8)                     1.3888(15)  
            C(7)-C(19)                    1.4050(16)  
            C(8)-C(9)                     1.4040(14)  
            C(8)-H(28)                    0.9300  
            C(9)-C(25)                    1.4183(16)  
            C(9)-C(10)                    1.4571(15)  
            C(11)-C(12)                   1.3716(14)  
            C(11)-C(26)                   1.4415(15)  
            C(12)-C(13)                   1.4163(16)  
            C(12)-H(22)                   0.9300  
            C(13)-N(1)                    1.3486(13)  
            C(13)-C(28)                   1.4527(15)  
            N(1)-C(15)                    1.3428(16)  
! 227!
            C(15)-C(16)                   1.4278(15)  
            C(15)-C(29)                   1.4345(16)  
            C(16)-C(17)                   1.3585(19)  
            C(16)-H(26)                   0.9300  
            C(17)-C(30)                   1.423(2)  
            C(17)-H(9)                    0.9300  
            C(18)-H(35)                   0.9600  
            C(18)-H(36)                   0.9600  
            C(18)-H(10)                   0.9600  
            C(19)-C(20)                   1.3948(15)  
            C(19)-H(29)                   0.9300  
            C(20)-C(25)                   1.4072(16)  
            C(20)-C(21)                   1.5378(16)  
            C(21)-C(23)                   1.5364(18)  
            C(21)-C(22)                   1.5402(18)  
            C(21)-C(24)                   1.5411(19)  
            C(22)-H(13)                   0.9600  
            C(22)-H(11)                   0.9600  
            C(22)-H(12)                   0.9600  
            C(23)-H(14)                   0.9600  
            C(23)-H(16)                   0.9600  
            C(23)-H(15)                   0.9600  
            C(24)-H(18)                   0.9600  
            C(24)-H(17)                   0.9600  
            C(24)-H(19)                   0.9600 
            C(26)-C(27)                   1.3691(15)  
            C(27)-C(28)                   1.4227(14)  
            C(27)-H(27)                   0.9300  
            C(29)-C(31)                   1.4170(17)  
            C(30)-C(31)                   1.3664(17)  
            C(30)-H(24)                   0.9300  
            C(31)-H(25)                   0.9300  
            C(32)-H(33)                   0.9600  
            C(32)-H(34)                   0.9600  
            C(32)-H(32)                   0.9600  
   
            C(25)-O(1)-H(20)            105.4(12)  
            H(37)-O(2)-H(38)            102.8(16)  
            C(4)-O(3)-C(3)              106.18(16)  
            C(10)-N(2)-C(11)            105.79(9)  
            C(10)-N(3)-C(26)            107.37(9)  
            C(10)-N(3)-H(21)            126.3  
            C(26)-N(3)-H(21)            126.3  
            C(28)-N(4)-C(29)            118.00(10)  
            C(4)-C(1)-C(2)              104.31(16)  
            C(4)-C(1)-H(1)              110.9  
! 228!
            C(2)-C(1)-H(1)              110.9  
            C(4)-C(1)-H(4)              110.9  
            C(2)-C(1)-H(4)              110.9  
            H(1)-C(1)-H(4)              108.9  
            C(3)-C(2)-C(1)              103.44(16)  
            C(3)-C(2)-H(6)              111.1  
            C(1)-C(2)-H(6)              111.1  
            C(3)-C(2)-H(5)              111.1  
            C(1)-C(2)-H(5)              111.1  
            H(6)-C(2)-H(5)              109.0  
            O(3)-C(3)-C(2)              107.16(16)  
            O(3)-C(3)-H(2)              110.3  
            C(2)-C(3)-H(2)              110.3  
            O(3)-C(3)-H(7)              110.3  
            C(2)-C(3)-H(7)              110.3  
            H(2)-C(3)-H(7)              108.5  
            O(3)-C(4)-C(1)              108.52(19)  
            C(6)-C(5)-H(31)             109.5  
            C(6)-C(5)-H(8)              109.5  
            H(31)-C(5)-H(8)             109.5  
            C(6)-C(5)-H(30)             109.5  
            H(31)-C(5)-H(30)            109.5  
            H(8)-C(5)-H(30)             109.5  
            C(5)-C(6)-C(7)              112.51(10)  
            C(5)-C(6)-C(18)             107.72(10)  
            C(7)-C(6)-C(18)             110.86(9)  
            C(5)-C(6)-C(32)             108.80(11)  
            C(7)-C(6)-C(32)             108.39(10)  
            C(18)-C(6)-C(32)            108.47(10)  
            C(8)-C(7)-C(19)             116.97(10)  
            C(8)-C(7)-C(6)              120.72(10)  
            C(19)-C(7)-C(6)             122.14(10)  
            C(7)-C(8)-C(9)              121.39(10)  
            C(7)-C(8)-H(28)             119.3  
            C(9)-C(8)-H(28)             119.3  
            C(8)-C(9)-C(25)             119.85(10)  
            C(8)-C(9)-C(10)             120.64(10)  
            C(25)-C(9)-C(10)            119.45(10)  
            N(2)-C(10)-N(3)             112.73(10)  
            N(2)-C(10)-C(9)             122.36(10)  
            N(3)-C(10)-C(9)             124.87(10)  
            C(12)-C(11)-N(2)            129.75(10)  
            C(12)-C(11)-C(26)           121.40(11)  
            N(2)-C(11)-C(26)            108.84(9)  
            C(11)-C(12)-C(13)           117.92(10)  
            C(11)-C(12)-H(22)           121.0  
! 229!
            C(13)-C(12)-H(22)           121.0  
            N(1)-C(13)-C(12)            118.67(10)  
            N(1)-C(13)-C(28)            121.00(11)  
            C(12)-C(13)-C(28)           120.32(10)  
            C(15)-N(1)-C(13)            117.50(10)  
            N(1)-C(15)-C(16)            119.69(11)  
            N(1)-C(15)-C(29)            121.61(10)  
            C(16)-C(15)-C(29)           118.69(11)  
            C(17)-C(16)-C(15)           120.16(12)  
            C(17)-C(16)-H(26)           119.9  
            C(15)-C(16)-H(26)           119.9  
            C(16)-C(17)-C(30)           121.20(11)  
            C(16)-C(17)-H(9)            119.4  
            C(30)-C(17)-H(9)            119.4  
            C(6)-C(18)-H(35)            109.5  
            C(6)-C(18)-H(36)            109.5  
            H(35)-C(18)-H(36)           109.5  
            C(6)-C(18)-H(10)            109.5  
            H(35)-C(18)-H(10)           109.5  
            H(36)-C(18)-H(10)           109.5  
            C(20)-C(19)-C(7)            124.40(10)  
            C(20)-C(19)-H(29)           117.8  
            C(7)-C(19)-H(29)            117.8  
            C(19)-C(20)-C(25)           117.22(11)  
            C(19)-C(20)-C(21)           121.90(10)  
            C(25)-C(20)-C(21)           120.87(10)  
            C(23)-C(21)-C(20)           111.74(10)  
            C(23)-C(21)-C(22)           107.34(11)  
            C(20)-C(21)-C(22)           110.25(10)  
            C(23)-C(21)-C(24)           107.41(11)  
            C(20)-C(21)-C(24)           110.19(11)  
            C(22)-C(21)-C(24)           109.83(11)  
            C(21)-C(22)-H(13)           109.5  
            C(21)-C(22)-H(11)           109.5  
            H(13)-C(22)-H(11)           109.5  
            C(21)-C(22)-H(12)           109.5  
            H(13)-C(22)-H(12)           109.5  
            H(11)-C(22)-H(12)           109.5  
            C(21)-C(23)-H(14)           109.5  
            C(21)-C(23)-H(16)           109.5  
            H(14)-C(23)-H(16)           109.5  
            C(21)-C(23)-H(15)           109.5  
            H(14)-C(23)-H(15)           109.5  
            H(16)-C(23)-H(15)           109.5  
            C(21)-C(24)-H(18)           109.5  
            C(21)-C(24)-H(17)           109.5  
! 230!
            H(18)-C(24)-H(17)           109.5  
            C(21)-C(24)-H(19)           109.5  
            H(18)-C(24)-H(19)           109.5  
            H(17)-C(24)-H(19)           109.5  
            O(1)-C(25)-C(20)            118.96(10)  
            O(1)-C(25)-C(9)             120.87(10)  
            C(20)-C(25)-C(9)            120.17(10)  
            C(27)-C(26)-N(3)            132.10(10)  
            C(27)-C(26)-C(11)           122.63(10)  
            N(3)-C(26)-C(11)            105.26(9)  
            C(26)-C(27)-C(28)           116.98(10)  
            C(26)-C(27)-H(27)           121.5  
            C(28)-C(27)-H(27)           121.5  
            N(4)-C(28)-C(27)            118.67(10)  
            N(4)-C(28)-C(13)            120.62(10)  
            C(27)-C(28)-C(13)           120.71(10)  
            N(4)-C(29)-C(31)            119.67(11)  
            N(4)-C(29)-C(15)            121.07(11)  
            C(31)-C(29)-C(15)           119.25(10)  
            C(31)-C(30)-C(17)           120.14(12)  
            C(31)-C(30)-H(24)           119.9  
            C(17)-C(30)-H(24)           119.9  
            C(30)-C(31)-C(29)           120.53(12)  
            C(30)-C(31)-H(25)           119.7  
            C(29)-C(31)-H(25)           119.7  
            C(6)-C(32)-H(33)            109.5  
            C(6)-C(32)-H(34)            109.5  
            H(33)-C(32)-H(34)           109.5  
            C(6)-C(32)-H(32)            109.5  
            H(33)-C(32)-H(32)           109.5  
            H(34)-C(32)-H(32)           109.5  
           _____________________________________________________________  
   
            
             
 
! 231!
 
Crystallographic Table 52 Anisotropic displacement parameters (?
 2
 x 10
3
) for 
t-butsalzine. The anisotropic displacement factor exponent takes the form: -2 ?^2 
[ h^2 a*^2 U11 + ... + 2 h k a* b* U12 ]  
   
    
_______________________________________________________________________  
   
              U11        U22        U33        U23        U13        U12  
    
_______________________________________________________________________  
   
    O(1)     40(1)      30(1)      42(1)      22(1)      24(1)      22(1)  
    O(2)     32(1)      27(1)      44(1)       7(1)      12(1)      15(1)  
    O(3)     75(1)      42(1)      58(1)      26(1)      16(1)       9(1)  
    N(2)     30(1)      21(1)      25(1)      10(1)      13(1)      11(1)  
    N(3)     26(1)      18(1)      24(1)      10(1)      12(1)       9(1)  
    N(4)     25(1)      20(1)      26(1)      11(1)      11(1)       7(1)  
    C(1)    107(2)      35(1)      71(1)      21(1)      41(1)      19(1)  
    C(2)     74(1)      56(1)      52(1)      28(1)      26(1)      27(1)  
    C(3)     88(2)      51(1)      60(1)      18(1)      24(1)      34(1)  
    C(4)    221(4)      39(1)      51(1)      10(1)      48(2)      -9(2)  
    C(5)     43(1)      37(1)      44(1)      27(1)      24(1)      20(1)  
    C(6)     27(1)      24(1)      24(1)      12(1)      10(1)      10(1)  
    C(7)     24(1)      21(1)      21(1)       8(1)       8(1)       8(1)  
    C(8)     25(1)      21(1)      22(1)       9(1)      11(1)      10(1)  
    C(9)     24(1)      20(1)      20(1)       8(1)       9(1)       8(1)  
    C(10)    24(1)      19(1)      20(1)       7(1)       8(1)       8(1)  
    C(11)    25(1)      18(1)      20(1)       7(1)       8(1)       7(1)  
    C(12)    28(1)      18(1)      25(1)       8(1)      11(1)      10(1)  
    C(13)    23(1)      15(1)      20(1)       6(1)       6(1)       6(1)  
    N(1)     28(1)      18(1)      25(1)       9(1)       8(1)       7(1)  
    C(15)    24(1)      18(1)      24(1)       8(1)       6(1)       5(1)  
    C(16)    35(1)      22(1)      33(1)      14(1)      11(1)       9(1)  
    C(17)    39(1)      27(1)      37(1)      19(1)      14(1)       8(1)  
    C(18)    34(1)      24(1)      30(1)       8(1)      10(1)      12(1)  
    C(19)    27(1)      22(1)      22(1)       8(1)      11(1)       8(1)  
    C(20)    25(1)      23(1)      23(1)       7(1)      10(1)       9(1)  
    C(21)    31(1)      25(1)      28(1)       8(1)      16(1)      12(1)  
    C(22)    31(1)      32(1)      38(1)      13(1)      16(1)      15(1)  
    C(23)    40(1)      39(1)      35(1)      16(1)      24(1)      18(1)  
    C(24)    48(1)      28(1)      37(1)       1(1)      21(1)      10(1)  
    C(25)    27(1)      21(1)      25(1)       8(1)      11(1)      12(1)  
    C(26)    22(1)      17(1)      20(1)       7(1)       6(1)       6(1)  
    C(27)    24(1)      17(1)      25(1)       9(1)       9(1)       8(1)  
    C(28)    21(1)      17(1)      21(1)       7(1)       6(1)       6(1)  
! 232!
    C(29)    22(1)      20(1)      24(1)       9(1)       7(1)       5(1)  
    C(30)    36(1)      32(1)      38(1)      20(1)      18(1)       8(1)  
    C(31)    31(1)      28(1)      36(1)      17(1)      18(1)      10(1)  
    C(32)    34(1)      34(1)      32(1)      10(1)       1(1)      11(1)  
    
_______________________________________________________________________  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
! 233!
Crystallographic Table 53 Hydrogen coordinates ( x 10
4
) and isotropic 
displacement parameters (?
 2
 x 10
3
) for t-butsalzine.  
   
         ________________________________________________________________  
   
                          x             y              z             U(eq)  
         ________________________________________________________________  
   
          H(20)        -940(20)      7030(20)      6758(13)        47  
          H(37)        7530(20)      7914(14)      4768(10)        50  
          H(38)        6198(11)      7140(20)      4246(12)        50  
          H(21)        2068           4552           5868            25  
          H(1)         3767          6713           9194            80  
          H(4)         1947           6359           9038            80  
          H(6)         2275           7874          10319            67  
          H(5)         4080           8325          10436            67  
          H(2)         1778           9594           9740            76  
          H(7)         3537          10321          10228            76  
          H(31)       -1158           1031           8136            53  
          H(8)           16           1964           9026            53  
          H(30)         310            523           8546            53  
          H(28)        1391           3575           6860           25  
          H(22)         753           9174           5488            26  
          H(26)        3024          11793           3791            34  
          H(9)         4420          11890           2804            38  
          H(35)        1419            276           7366            42  
          H(36)        1553           1427           6863            42  
          H(10)         -86            540           6797            42  
          H(29)       -1356           3371           8436            26  
          H(13)       -4795           4348           7334            47  
          H(11)       -4092           5765           7164            47  
          H(12)       -5004           5789           7871            47  
          H(14)       -3585           3684           8629           51  
          H(16)       -3958           5028           9181           51  
          H(15)       -2267           4783           9399           51  
          H(18)       -2850           7372           9137            57  
          H(17)       -1991           7615           8437            57  
          H(19)       -1153           7154           9240            57  
          H(27)        3569           5669           4763            24  
          H(24)        5683          10094           2372            39  
          H(25)        5553           8211           2949            34  
          H(33)        2473           3501           9064            52  
          H(34)        3131           3187           8251            52  
          H(32)        2960           2068           8774            52  
         ________________________________________________________________  
 
! 234!
 
 
         Crystallographic Table 54 Torsion angles [?] for t-butsalzine.  
         ________________________________________________________________  
   
          C(4)-C(1)-C(2)-C(3)                                    4.7(3)  
          C(4)-O(3)-C(3)-C(2)                                   33.2(3)  
          C(1)-C(2)-C(3)-O(3)                                  -22.7(2)  
          C(3)-O(3)-C(4)-C(1)                                  -30.1(3)  
          C(2)-C(1)-C(4)-O(3)                                   15.2(4)  
          C(5)-C(6)-C(7)-C(8)                                 -169.03(11)  
          C(18)-C(6)-C(7)-C(8)                                 -48.33(14)  
          C(32)-C(6)-C(7)-C(8)                                 70.62(14)  
          C(5)-C(6)-C(7)-C(19)                                  15.73(16)  
          C(18)-C(6)-C(7)-C(19)                                136.43(12)  
          C(32)-C(6)-C(7)-C(19)                               -104.62(13)  
          C(19)-C(7)-C(8)-C(9)                                   0.34(17)  
          C(6)-C(7)-C(8)-C(9)                                 -175.14(10)  
          C(7)-C(8)-C(9)-C(25)                                  -0.16(17)  
          C(7)-C(8)-C(9)-C(10)                                 177.06(10)  
          C(11)-N(2)-C(10)-N(3)                                 -0.93(13)  
          C(11)-N(2)-C(10)-C(9)                                176.96(10)  
          C(26)-N(3)-C(10)-N(2)                                 0.76(13)  
          C(26)-N(3)-C(10)-C(9)                               -177.07(10)  
          C(8)-C(9)-C(10)-N(2)                                -170.48(11)  
          C(25)-C(9)-C(10)-N(2)                                  6.75(17)  
          C(8)-C(9)-C(10)-N(3)                                   7.15(17)  
          C(25)-C(9)-C(10)-N(3)                               -175.62(11)  
          C(10)-N(2)-C(11)-C(12)                              -178.25(12)  
          C(10)-N(2)-C(11)-C(26)                                 0.73(12)  
          N(2)-C(11)-C(12)-C(13)                               178.79(11)  
          C(26)-C(11)-C(12)-C(13)                               -0.08(17)  
          C(11)-C(12)-C(13)-N(1)                              -177.59(10)  
          C(11)-C(12)-C(13)-C(28)                                1.65(17)  
          C(12)-C(13)-N(1)-C(15)                              -176.68(10)  
          C(28)-C(13)-N(1)-C(15)                                 4.08(16)  
          C(13)-N(1)-C(15)-C(16)                               177.11(10)  
          C(13)-N(1)-C(15)-C(29)                                -1.89(17)  
          N(1)-C(15)-C(16)-C(17)                              -177.29(12)  
          C(29)-C(15)-C(16)-C(17)                                1.73(18)  
          C(15)-C(16)-C(17)-C(30)                               -1.1(2)  
          C(8)-C(7)-C(19)-C(20)                                 -0.48(17)  
          C(6)-C(7)-C(19)-C(20)                                174.93(11)  
          C(7)-C(19)-C(20)-C(25)                                 0.40(18)  
          C(7)-C(19)-C(20)-C(21)                              -178.39(11)  
          C(19)-C(20)-C(21)-C(23)                                0.45(17)  
! 235!
          C(25)-C(20)-C(21)-C(23)                             -178.30(11)  
          C(19)-C(20)-C(21)-C(22)                             -118.83(12)  
          C(25)-C(20)-C(21)-C(22)                               62.42(15)   
          C(25)-C(20)-C(21)-C(24)                             -58.97(15)  
          C(19)-C(20)-C(25)-O(1)                              -179.75(10)  
          C(21)-C(20)-C(25)-O(1)                                -0.95(17)  
          C(19)-C(20)-C(25)-C(9)                                -0.19(17)  
          C(21)-C(20)-C(25)-C(9)                               178.61(11)  
          C(8)-C(9)-C(25)-O(1)                                 179.63(10)  
          C(10)-C(9)-C(25)-O(1)                                  2.38(17)  
          C(8)-C(9)-C(25)-C(20)                                  0.08(17)  
          C(10)-C(9)-C(25)-C(20)                              -177.17(10)  
          C(10)-N(3)-C(26)-C(27)                               180.00(12)  
          C(10)-N(3)-C(26)-C(11)                                -0.25(12)  
          C(12)-C(11)-C(26)-C(27)                               -1.43(17)  
          N(2)-C(11)-C(26)-C(27)                               179.48(10)  
          C(12)-C(11)-C(26)-N(3)                               178.79(10)  
          N(2)-C(11)-C(26)-N(3)                                 -0.30(12)  
          N(3)-C(26)-C(27)-C(28)                              -179.07(11)  
          C(11)-C(26)-C(27)-C(28)                                1.22(16)  
          C(29)-N(4)-C(28)-C(27)                               178.34(10)  
          C(29)-N(4)-C(28)-C(13)                                -2.05(16)  
          C(26)-C(27)-C(28)-N(4)                               179.99(10)  
          C(26)-C(27)-C(28)-C(13)                                0.38(16)  
          N(1)-C(13)-C(28)-N(4)                                 -2.23(17)  
          C(12)-C(13)-C(28)-N(4)                               178.55(10)  
          N(1)-C(13)-C(28)-C(27)                               177.37(10)  
          C(12)-C(13)-C(28)-C(27)                               -1.85(16)  
          C(28)-N(4)-C(29)-C(31)                              -176.22(10)  
          C(28)-N(4)-C(29)-C(15)                                 4.26(17)  
          N(1)-C(15)-C(29)-N(4)                                -2.40(18)  
          C(16)-C(15)-C(29)-N(4)                               178.60(11)  
          N(1)-C(15)-C(29)-C(31)                               178.08(11)  
          C(16)-C(15)-C(29)-C(31)                               -0.92(17)  
          C(16)-C(17)-C(30)-C(31)                               -0.4(2)  
          C(17)-C(30)-C(31)-C(29)                                1.2(2)  
          N(4)-C(29)-C(31)-C(30)                               179.94(12)  
          C(15)-C(29)-C(31)-C(30)                               -0.53(19)  
         ________________________________________________________________