The Pennsylvania State University the Graduate School Eberly

The Pennsylvania State University

The Graduate School

Eberly College of Science

THE TETRA-DECKER SANDWICH: A NOVEL ION IN THE CLASS OF ZINTL IONS

CONTAINING ARSENIC CLUSTERS

A Thesis in

Chemistry

Darlene S. Biziak

Submitted in Partial Fulfillment of the Requirements for the Degree of

Master of Science

August 2009

The thesis of Darlene S. Biziak was reviewed and approved* by the following:

Ayusman Sen Professor and Head of Chemistry Thesis Adviser

John V. Badding Professor of Chemistry

A. W. Castleman, Jr. Evan Pugh Professor of Chemistry and Physics Eberly Distinguished Chair in Science

*Signatures are on file in the Graduate School.

ABSTRACT

This thesis is focused on a new ion formed in the field of cluster-based materials synthesis.

Arsenic clusters have been used extensively in new materials synthesis because of the flexibility they can provide in materials with novel electronic and optical properties. Chapter 1 of this thesis discusses Zintl ions, the class of compound to which arsenic clusters belong. It discusses how the various properties may be changed in order to synthesize new materials. Chapter 2 explains the synthetic route to making the tetra-decker sandwich compound, a novel compound formed during development of new materials containing arsenic clusters. Chapter 3 compares our novel structure to some of the known structures which resemble the tetra-decker sandwich, namely some triple-decker sandwiches. A discussion of similarities and differences shows the novelty of our compound in comparison to others.

iii

TABLE OF CONTENTS

List of Tables……………………………………………………………………………………...v

List of Figures………………………………………………………………………………….....vi

Acknowledgments……………………………………………………………………………….vii

Chapter 1. INTRODUCTION……………………………………………………………………..1

Chapter 2. SYNTHETIC ROUTE TO MAKING THE TETRA-DECKER SANDWICH.….....11

Chapter 3. RESULTS AND DISCUSSION……………………………………………………..12

3.1 The Tetra-decker Sandwich………………………………………………………….12

3.2 Some Triple-decker Sandwiches…………………………………………………….19

3.3 Similarities and Differences among Sandwiches…………………………………....30

Chapter 4. CONCLUSION………………………………………………………………………32

Appendix A. BOND LENGTHS OF SANDWICHES…………………………………………..33

Appendix B. BOND ANGLES OF SANDWICHES………………………………………….....38

LIST OF FIGURES

Figure 1-1: Various crown ethers…………………………………………………………...…….3

Figure 1-2: Crypt[2.2.2]………………………………………..……………………………….....4

Figure 1-3: Dimensionality seen in crystal structures……………………………………………..7

Figure 1-4: HOMO-LUMO Gap and Band Gap Illustration……………………………………...9

3- Figure 3-1: Structure of As11 cluster formed in one phase………………………...…………...13

Figure 3-2: View of crystal………………………………………………………………………15

Figure 3-3: Structure of Tetra-Decker Sandwich with Arsenic Clusters………………………...17

Figure 3-4: a) [Cs2(18-crown-6)3][H(cbto)2]2·2Hcbto·2H2O b) H(cbto)2 and 2Hcbto·2H2O...... 20

Figure 3-5: [(18-crown-6)Na(18-crown-6)Na(18-crown-6)] (Ph4C5H1)2…...... 23

Figure 3-6: [Cs(benzo-18-crown-6)2]I3...... 26

Figure 3-7: a) [Cs2(benzo-18-crown-6)3](I3)2 b) Packing of [Cs2(benzo-18-crown-6)3](I3)2…....28

LIST OF TABLES

Table 3-1: Crystal Data and Structure Refinement Parameters for [Cs3(18-C-6)4]As11…………18

Table 3-2: Crystal Data and Structure Refinement Parameters for [Cs2(18-crown-6)3] [H(cbto)2]2·2Hcbto·2H2O...... 21

Table 3-3: Crystal Data and Structure Refinement Parameters for [Na2(18-c-6)3] (Ph4C5H1)2….24

Table 3-4: Crystal Data and Structure Refinement Parameters for [Cs(benzo-18-crown-6)2]I3...27

Table 3-5: Crystal Data and Structure Refinement Parameters for [Cs2(benzo-18-crown-6)3](I3)2…………………………………………………………………..29

Table 3-6: Selected Bond Angles for Sandwiches……………………………………………….31

ACKNOWLEDGEMENTS

I would like to start off by thanking Dr. Ayusman Sen for his support throughout my time at Penn State. He has been a great scientific mentor and motivator. I would also like to thank my committee members, Dr. John V. Badding and Dr. A. W. Castleman for their contributions to my work and for their valuable time spent on my committee. I must also thank Dr. Hemant

Yennawar for his assistance with crystallography, both in knowledge and advice.

Much thanks goes to Dr. Angel Ugrinov and Matthew Dirmyer for their help. They have taught me many valuable experimental skills needed to pursue my research here at Penn State.

They have been a valuable asset in my skills as a researcher. I also want to thank the remaining members of the Sen group, both past and present, for making my time at Penn State enjoyable.

Thanks also goes to the following people: Weinan Chen, BettyJo Houser, Rong Luo,

Patty Nguyen, Claire van Ogtrop, Jenay Robert, Ran Tu, Dr. Will Wadlington, and Christopher

Wostenberg. Without support from each of these people, my graduate studies at Penn State would be an impossible journey. I am grateful for the contributions each of these people have made to my life here at Penn State and for their support during the chaotic times.

I also want to thank my family. I would first like to thank my mom, Janina Biziak, for always being there for me and giving me the advice of a wise woman. I am grateful for her love and support. Next, I would like to thank my sister, Renee Biziak-DiNinno. She is like a second mother to me and a best friend by giving me valuable advice and support. Without her, life would be not as enjoyable. Next, I thank my brother, Jason Biziak, for always having faith in me and trying to nudge me into the right direction. I am also grateful to my dad, John Biziak, for his support. I also want to thank the late Stephanie Furtak. I will miss her always and am grateful for her motherly love and support throughout the years that we were together. I would also like to

vii thank the rest of my family from cousins to aunts and uncles to everyone else for their support; it has not been overlooked.

Everyone mentioned here has guided my life in a more positive direction and for that, I am grateful. I wish them all the best in all their endeavors.

viii

Chapter 1

BACKGROUND INTRODUCTION

Metal clusters have been seen as a good resource for new materials. A single cluster has the ability to form in many different ways and thus provides for tunability of a material which is made from clusters. This is important for new technologies because if a new device requires a specialized property in a certain working range, perhaps one of these new materials can be made for such purposes. Alternatively, new devices can be developed using these new materials which may improve current technology by allowing for a broader working range. Our research focuses on developing new materials using clusters, specifically those of arsenic, but other metals in the p-block are also being considered. Aluminum is an example of one of those metals of interest because it is believed to have useful properties in optics and electronics and is also non-toxic.

Eduard Zintl started his research working with intermetallic compounds in 1928. He studied the structure of complex anions formed by metals in a solution of sodium in ammonia. In his studies, he discovered that new phases containing anionic metal clusters exist which mimic regular ionic bonding and the structure of these clusters should be similar to an isoelectronic element. These phases contain two parts: one is a homoatomic metal cluster which is usually anionic in nature and the other is a stabilizing agent used for crystallization which is usually cationic. In his experiments, Zintl discovered anion clusters of arsenic, tin, sulfur, and lead. Since then, many other clusters have been discovered containing various p-block metals. These clusters are known as Zintl ions.

The definition of a Zintl ion has been described by many. Since Zintl ion elements are positioned between the intermetallics (a combination of two or more metallic or semimetallic elements) and insulating valence compounds (two non-metals) on the periodic table1, it is hard to

come up with a strict set of classifications that describe them well since some overlap occurs. A common theme seen among these definitions is that their crystal structures contain a group I or group II metal cation and some sequestering agent alongside an anionic metal cluster. The sequestering agent acts as a stabilizer by capturing the smaller cation to make a larger cation that is comparable in size to the anion. This aids in crystallization, but is not necessary for their formation in solution. Commonly seen sequestering agents are crown ethers and cryptand-222.

Examples of these can be seen in figures 1-1 and 1-2.

Figure 1-1: Various crown ethers2

Figure 1-2: Crypt[2.2.2]3

When a Zintl phase forms, it is necessary that the cation and the anion of the solid be about the same size. This is so that the crystal does not collapse. Uneven balances will either not form crystals or form very brittle ones. The anion of the phase, or Zintl ion, usually consists of p-block elements in clusters of different shapes and sizes. Common examples of Zintl ions are arsenic

3- 3- clusters, specifically As7 and As11 clusters.

Each unique cluster is known as a building block. Many different materials have been

3- 3- seen using the same building block. The building blocks of interest to us are As7 and As11 clusters. Cluster materials can be tuned in a few different ways. One source of tunability is to change the position in space which the clusters occupy (i.e. rotate them) with regard to the overall structure. This can be related to polarization. A chiral solution can polarize light due to the differences in the composition of a solution. If the clusters are rotated when compared to each other, they may exhibit different optical properties like a chiral solution.

Another source of tunability is to assemble the materials using different substances

(building blocks or cations). Since it is known that different elements exhibit different properties, one can speculate that new properties can be developed if the composition of the material changes with a change in building block cluster or the cation of these materials.

A third source of tunability with regard to these materials is seen in the crystallization.

These materials can exhibit different interactions in their 0-D, 1-D, 2-D, or 3-D directions. This means that materials can show interactions between clusters, strands, layers etc.

When a cluster exhibits 0-D interactions, there is no interaction seen between a cluster and any other part of the crystal. This means that the clusters are separate entities from everything else in the crystal. In a 1-D interaction, there is some regularity seen but, the strands

(e.g. chains or helices.) do not show interaction between strands, but only within a strand. To illustrate, the clusters may interact with an atom (such as gadolinium as seen in figure 1-3) and make a chain of some sort. This is in contrast to 2-D interactions where the strands interact with each other either through solvent molecules that may be present or other components of the crystal. A 3-D interaction shows that there is interaction between layers and strands. All of the different interactions in the different dimensions allows for unique properties to be developed in the hopes that useful materials can be made.

Figure 1-3: Dimensionality seen in crystal structures3

One property currently being explored in relation to tunability of cluster materials is a material’s band gap. A HOMO-LUMO gap is the space between the highest occupied molecular orbital and the lowest unoccupied molecular orbital in a molecule with few atoms (see figure 1-4, left). When there are numerous amounts of atoms, such as in a solid material, there are many

HOMO-LUMO gaps present (see figure 1-4, right). These gaps overlap to form a virtuously continuous band since their molecular orbitals are so closely spaced in energy. This is what is known as a band gap. In our research, we are concerned with the band gaps of cluster-based materials and how they can be manipulated to produce materials which have the properties we are looking for.

Figure 1-4: HOMO-LUMO Gap and Band Gap Illustration 4

Materials with different band gaps are interesting because they may be used in new applications involving optics and electronics which is a large focus of our research. Since the clusters can form in similar ways, similar materials have shown a vast range of band gap values with changes to orientation in space of the clusters. Band gaps can also differ due to the composition of the material. Slight changes to structure such as containing different group I metals inside a sequestering agent, will only change band gaps slightly, whereas large changes, such as cations or anions with vastly different structures, can change the gaps tremendously.

Changing the band gap thus provides us with a wide range of values to work with.

In our work trying to synthesize useful new materials, we have discovered a new ion. The structure discussed here represents the first structure of its type, the first tetra-decker “sandwich complex” (so called due to its resemblance of layers much like the food) containing arsenic clusters. It is also the first quadruple decker sandwich to have naked clusters within it.

The term sandwich compound was introduced in organometallic nomenclature during the

1950s when Keally, Pauson and Miller first published the structure of ferrocene in 1951. Since then a variety of sandwich compounds has been developed. Half sandwich compounds such as

Grubb’s catalyst have also proven to be useful. Many sandwich compounds have been seen in research related to anti-cancer agents. Since arsenic is known to be toxic to living creatures, this

Zintl phase’s use as an anti-cancer agent is unlikely, however, its use as a material in an electronic or optical device may prove to be useful. Since their discovery, sandwich molecules have shown their potential in various applications.

Chapter 2

SYNTHETIC ROUTE TO MAKING THE TETRA-DECKER SANDWICH

All manipulations were carried out under an argon atmosphere in an mBraun glove box. All crystal analysis was performed by covering the crystals with Paratone-N (Hamilton Research), a

viscous oil that prevents contact with air. All crystal analysis was performed on a Bruker Apex

x-ray diffractometer using Mo K-α radiation and analyzed using Shelxtl Version 6.10.

Cesium (99.9+ %) was obtained from Strem Chemicals Inc. Liquid cesium metal is used as is

since it is sealed up and does not react with ethylenediamine gas in the glove-box the way that potassium does. Potassium can also be used to form arsenic clusters, however different structures

will be made. Ethylenediamine (Sigma-Aldrich, redistilled, 99.5+%) is then added to the group I

metal and the mixture is allowed to stir overnight to dissolve as much cesium as possible. The

solution is then filtered using a syringe filter to remove the by-products of the reaction. Arsenic

metal is now added to the mixture and the solution is left to stir for 1 hour. This solution was

then separated into two different reactions. 18-crown-6 (TCI America, 98%) was then added in a

molar ratio of 1:2 and 1:0.666 with cesium to the two reactions. The solution is then allowed to

sit without movement so that crystal formation can take place. From the second reaction, crystals

3- formed and a quadruple-decker sandwich of 18-crown-6 incorporating cesium atoms with As11

clusters was seen.

Chapter 3

RESULTS AND DISCUSSION

3.1 The Tetra-decker Sandwich

In an attempt to see if the amount of sequestering agent would make a difference in

structure, 2 reactions containing 18-crown-6 and cesium in different ratios were carried out. The

reactions that were performed contained a molar ratio of 1:2 18-crown-6: Cs and a 1:0.666 molar

ratio of Cs: 18-crown-6. From the second reaction, we obtained two phases. One phase was an

3- already known phase containing As11 clusters. This was determined by x-ray crystallography

and the structure of this phase can be seen below in figure 3-1.

3- Figure 3-1: Structure of As7 cluster formed in one phase

The other phase was the more interesting of the two. While there have been some examples of sandwich complexes seen before, these examples contain either only triple-decker sandwiches which have similar sequestering agents with group I metals, transition metals or p- block metals with benzene rings, or cyclopentadiene rings as equivalents to the sequestering agent with some transition metal between the rings. The compound seemed of interest to us due to the rare shape of the crystal seen. A photo of this crystal can be seen in figure 3-2.

Figure 3-2: View of crystal

The hexagonal nature of the crystal seemed as though the material may be unique due to the rare structure of the crystal found in the vial, so we decided to examine it. The compound discovered is the first example of a tetra-decker sandwich with naked metal clusters as the anion. As can be seen in figure 3-3, the structure of the new molecule is a four layered sandwich of 18-crown-6

3- and cesium as the cation and As11 as the anion. The crystal data and structure refinement properties can be found in table 3-1 on page 18.

Figure 3-3: Structure of [Cs3(18-crown-6)4]As11

Table 3-1: Crystal Data and Structure Refinement Parameters for [Cs3(18-crown-6)4]As11

Empirical Formula C48H96As11Cs3O24

Formula Weight 2280.10

Crystal System Rhombohedral (trigonal)

Space Group R-3c

a (Å) 16.437(3)

b(Å) 16.437(3)

c(Å) 46.346(14)

α 90.00

β 90.00

γ 120.00

Volume (Å3) 10844(4)

Z 6

T(K) 123(2)

Θ 1.68 to 28.27

Reflections collected 2959

Unique Reflections 2836

Number of Parameters 211

Goodness of Fit (S) 1.346

R (all data) R1 = 0.0412 wR2 = 0.0951

3.2 Some Triple-decker Sandwiches

One compound in the literature which is similar in structure to our molecule is [tris(18-

crown-6)-dicesium] [α-cyanobenzothiazole-α-carbaldehyde oxime] ([Cs2(18-crown-

6)3][H(cbto)2]2·2Hcbto·2H2O). This compound is very similar to ours in that it contains the same

building blocks in its sandwich cation, namely cesium ions and 18-crown-6 molecules. However,

there are a few differences. The first of these differences between our molecule and this one is

the number of layers in the sandwich. This compound has five layers and ours has seven (where

one 18-crown-6 or group I metal counts as one layer). Another difference is the counter-cation.

In [Cs2(18-crown-6)3][H(cbto)2]2·2Hcbto·2H2O the anion is the organic ion α- cyanobenzothiazole-α-carbaldehyde oxime (i.e.[H(cbto)2]2) whereas our structure contains an

inorganic metal cluster as the anion. These differences will without a doubt produce materials with differing properties. The entire structure of [Cs2(18-crown-6)3][H(cbto)2]2·2Hcbto·2H2O can be seen below in figure 3-4a and the cation can be seen in figure 3-4b, and the crystal data and structure refinement parameters can be seen following the structure diagram in table 3-2.

Figure 3-4: a) Triple-decker sandwich containing cesium and 18-crown-6 [Cs2(18-crown- 6 6)3][H(cbto)2]2·2Hcbto·2H2O b) H(cbto)2 and 2Hcbto·2H2O

Table 3-2: Crystal Data and Structure Refinement Parameters for [Cs2(18-crown- 6 6)3][H(cbto)2]2·2Hcbto·2H2O

Empirical Formula C90H104O26N18Cs2S6

Formula Weight 2312.1

Crystal System Triclinic

Space Group P-1 a (Å) 10.598(2) b(Å) 13.465(3) c(Å) 20.235(4)

α 75.31(3)°

β 89.99°

γ 71.42(3)°

Volume (Å3) 2637.4(9)

Z 1

T(K) N/A

Θ 1.0-22.5

Reflections collected 7349

Unique Reflections 6896

Number of Parameters 656

Goodness of Fit (S) 1.082

R (all data) 0.0067

Another example of these sandwich compounds is the compound tris(18-crown-6)- disodium bis(tetraphenylcyclopentadienide) ([Na2(18-crown-6)3][Ph4C5H1]2). This is also very similar to our compound in that it contains 18-crown-6 and a group I cation in its cation sandwich, but once again there are a few differences. This sandwich is much like the previous literature example in that it is a triple-decker sandwich, but differs from the previous literature example in that the sandwich contains sodium ions as the cations where the previous example contained cesium ions. Also like the previous literature example, the anion here is an organic ion.

So this structure differs from our structure in that it also has a different sized sandwich, the cations in the sandwich differ from ours, and the anion is an organic ion whereas our anion is an inorganic metal cluster. These differences, like that of the previous literature examples will cause the materials made from these building blocks to be different from those of our structure since the electronic structures also differ from each other. The structure of [Na2(18-crown-

6)3][Ph4C5H1]2 can be seen below in figure 3-5 and the crystal data and structure refinement parameters can be seen in table 3-3 on page 24.

Figure 3-5: [Na2(18-c-6)3] (Ph4C5H1)2

Table 3-3: Crystal Data and Structure Refinement Parameters for [Na2(18-c-6)3] (Ph4C5H1)2

Empirical Formula C106 H142 Na2O18

Formula Weight 1750.18

Crystal System Triclinic

Space Group P-1 a (Å) 10.6214(9) b(Å) 13.5910(10) c(Å) 18.572(2)

α 105.069(6)°

β 94.731(7)°

γ 110.677(4)°

Volume (Å3) 2376.53

Z 1

T(K) 150(2)

Θ 2.11-24.00

Reflections collected 7193

Unique Reflections 5478

Number of Parameters 559

Goodness of Fit (S) 1.053

R (all data) 0.0653

A third pair of examples of these sandwich complexes are seen with bis(18-crown-6)-

cesium (triiodide) ([Cs(benzo-18-crown-6)2]I3) and tris(18-crown-6)-dicesium bis(triiodide)

([Cs2(benzo-18-crown-6)3](I3)2). These two sandwich compounds are very similar to our

compound as the previous literature examples were. They differ from all the molecules thus far

discussed in that they have an anion which contains only a few atoms (3 or 6). The anions are still comparable in size to all the other structures but contain bigger atoms. These sandwiches also contain triple-decker sandwich cations which use cesium but contain a derivative of crown ether: benzo-18-crown-6. Benzo-18-crown-6 should only cause a slight difference between sandwiches since the benzene rings are electrophilic and will cause a slight difference in electronegativity. All of the differences between these structures and ours will cause differences in properties. Their structures can be seen in the two figures (figures 3-6 and 3-7) below. The crystal data and structure refinement parameters are also listed below the figures in tables 3-4 and 3-5.

8 Figure 3-6: [Cs(benzo-18-crown-6)2]I3

8 Table 3-4: Crystal Data and Structure Refinement Parameters for [Cs(benzo-18-crown-6)2]I3

Empirical Formula C32H48O12CsI3

Formula Weight 1138.31

Crystal System Monoclinic

Space Group C2/c

a (Å) 20.488(5)

b(Å) 13.295(5)

c(Å) 15.887(5)

α 110.23°

β 110.23°

γ 110.23°

Volume (Å3) 4061.0(9)

Z 4

T(K) 170(2)

Θ N/A

Reflections collected 30768

Unique Reflections 4502

Number of Parameters 3844

Goodness of Fit (S) 1.077

R (all data) 0.0372

8 8 Figure 3-7: a) [Cs2(benzo-18-crown-6)3](I3)2 b) Packing of [Cs2(benzo-18-crown-6)3](I3)2

8 Table 3-5: Crystal Data and Structure Refinement Parameters for [Cs2(benzo-18-crown-6)3](I3)2

Empirical Formula C48H72O18Cs2I6

Formula Weight 1964.28

Crystal System Monoclinic

Space Group C2/c

a (Å) 22.960(1)

b(Å) 20.937(1)

c(Å) 13.736(1)

α 100.21°

β 100.21°

γ 100.21°

Volume (Å3) 6495.3(5)

Z 4

T(K) 170(2)

Θ N/A

Reflections collected 34781

Unique Reflections 7079

Number of Parameters 6172

Goodness of Fit (S) 1.078

R (all data) 0.0341

3.3 Similarities and Differences among Sandwiches

All of the differences seen among these structures, although not experimentally

determined, will change the properties of the material. One can speculate this based on the

knowledge that the chemistries of the individual elements have been shown to exhibit different

properties themselves. This illustrates the possibility for a wide range of materials with different

properties to be developed and tuned to the needs of a researcher.

In a closer comparison of these structures’ sandwiches, one can see that there are

differences between the bond lengths in each of these sandwiches. An obvious difference is with

the structure determined by Bock versus the others. At first glance, there is a noticeable

difference in Bock’s structure in that this structure contains sodium as the group I cation not

cesium like the others. This will without a doubt produce a difference in bond length between the

group I metal and the oxygen of the crown ether when compared with the other cation

sandwiches. As can be seen in table 3-6, the bond lengths are in fact much shorter for the

sodium-oxygen bonds than the cesium-oxygen bonds in the other sandwiches. All the lengths between the cation and the 18-crown-6 molecules are markedly shorter here because sodium ions have a smaller radius and can actually fit within the crown ether’s cavity whereas cesium cannot.

Cesium ions will just coordinate to the oxygens of the crown ether and “sit on top” of the ring.

This is to be expected of differing cations and is exemplified here.

Table 3-6: Alkali Metal Oxygen Bond Lengths of Sandwich Compounds

a) [Cs3(18‐crown‐ b) [Cs2(18‐crown‐ c) [Na2(18‐crown‐ d) [Cs(benzo‐18‐ e) [Cs2(benzo‐18‐ 6)4] As11 6)3][H(cbto)2]2 6)3] (Ph4C5H1)2 crown‐6)2]I3 crown‐6)3](I3)2 ∙2Hcbto∙2H2O Bond Bond Bond Bond Bond Bond Bond Bond Bond Bond Type Length Type Length Type Length Type Length Type Length CS1- 3.154 Cs-O(4) 3.636(5) Na(1)- 2.675(3) Cs1-O1 3.361(3) Cs1- 3.408(3) O11 O(1) O101 CS1- 3.154 Cs- 3.416(5) Na(1)- 2.640(11) Cs1-O1 3.361(3) Cs1- 3.535(3) O11 O(4a) O(2) O101 CS1- 3.216 Cs-O(5) 3.393(5) Na(1)- 2.571(2) Cs1-O4 3.256(2) Cs1- 3.263(2) O12 O(3) O104 CS1- 3.216 Cs- 3.636(5) Na(1)- 2.589(2) Cs1-O4 3.256(2) Cs1- 3.741(3) O12 O(5a)* O(4) O104 CS1 - 3.216 Cs-O(6) 3.546(5) Na(1)- 2.695(2) Cs1-O7 3.290(3) Cs1- 3.429(3) O12 O(5) O107 CS1- 3.426 Cs- 3.442(5) Na(1)- 2.517(2) Cs1-O7 3.290(3) Cs1- 3.527(3) O21 O(6a)* O(6) O107 CS1- 3.426 Cs-O(7) 3.152(7) Na(1)- 2.445(2) Cs1-O10 3.241(4) Cs1- 3.288(2) O21 O(7) O201 CS1- 3.426 Cs-O(8) 3.397(7) Na(1)- 2.559(2) Cs1-O10 3.241(4 Cs1- 3.164(2) O21 O(8) O204 CS2- 3.518 Cs-O(9) 3.182(7) Cs1-O13 3.273(3) Cs1- 3.282(3) O21 O207 CS2- 3.518 Cs- 3.220(7) Cs1-O13 3.273(3) Cs1- 3.122(4) O21 O(10) O210 CS2- 3.518 Cs- 3.413(8) Cs1-O16 3.303(3) Cs1- 3.214(3) O21 O(11) O213 CS2- 3.518 Cs- 3.227(7) Cs1-O16 3.303(3) Cs1- 3.316(3) O21 O(12) O216 CS2- 3.518 O21 CS2- 3.455 O22 CS2- 3.455 O22

Another noticeable difference between the sandwiches is that the triple-decker sandwiches and the tetra-decker sandwich is that the triple-decker sandwiches only have one type of cesium (or sodium in the case where sodium is the cation) whereas the quadruple-decker sandwich has two: the two outer cations and the middle cation. The bond lengths show that for

Cs(2) in the quadruple-decker sandwich, the lengths seem to be longer than for Cs(1). This longer bond distance is most likely due to a stronger pull of the two crown ethers on either side of Cs(2).

Another difference seen in the bond length data seems to be that the tetra-decker sandwich has more symmetry than the triple-decker sandwiches. This can be seen in the lengths of the different cesium atoms with oxygen. The data shows that each bond between Cs(1) and

O(11) have values which are exactly the same. This can be seen among the other cesium-oxygen bonds in the tetra-decker sandwich as well. The triple-decker sandwiches bond lengths differ from one another either slightly or majorly which makes for less symmetry in the molecules.

Bond angles are also a topic to be discussed. The bond angle data of these molecules confirm the idea that the tetra-decker sandwich is more symmetrical than the other sandwiches shown. The bond angles are seen to be exactly the same for most bonds in the tetra-decker sandwich. The triple-decker sandwiches do not show this kind of symmetry and have more noticeable bond angles differences. The angles for the triple-decker sandwiches are still relatively similar, but because they lack the strict symmetry exhibited by the tetra-decker sandwich, they are more pronounced in their differences. The bond angles for each molecule can be seen in Appendix B.

Chapter 4

Conclusion

In our studies of arsenic Zintl ions, we have discovered a novel cation. This cation, a tetra-decker sandwich containing 18-crown-6 and cesium atoms, is the first of its kind. It is the first tetra-decker sandwich to containing arsenic clusters and it is the first tetra-decker sandwich to have naked clusters.

Other sandwich cations have been seen, but most of these structures are triple-decker sandwiches as the ones shown in this thesis. The cations of these Zintl phases also are generally organic in nature such as those studied by Domasevitch or they vary in structure in that they do not contain a sequestering agent such as the structures studied by Herzmann containing triiodide.

APPENDIX A

Bond Lengths of Presented Sandwiches

Table A-1: Bond Lengths for [Cs3(18-crown-6)4]As11

Atom 1 Atom 2 Length Cs2 O21 3.518(4) Cs1 O11 3.154(3) Cs2 O21 3.518(4) Cs1 O11 3.154(3) Cs2 O21 3.518(4) Cs1 O11 3.154(3) Cs2 O21 3.518(4) Cs1 O12 3.216(3) O21 C201 1.407(10) Cs1 O12 3.216(3) O21 C203 1.410(11) Cs1 O12 3.216(3) O22 C202 1.426(11) Cs1 O21 3.426(4) O22 C204 1.427(12) Cs1 O21 3.426(4) C201 C204 1.472(17) Cs1 O21 3.426(4) C202 C203 1.483(16) Cs1 O22 3.808(4) C203 C202 1.483(16) Cs1 O22 3.808(4) C204 C201 1.472(17) Cs1 O22 3.808(4) As1 As21 1.662(3) O11 C102 1.434(6) As1 As21 1.662(3) O11 C101 1.434(6) As1 As2 2.383(5) O12 C103 1.427(5) As1 As2 2.383(5) O12 C104 1.434(6) As11 As2 1.665(4) C101 C104 1.504(7) As11 As2 1.665(4) C102 O11 1.434(6) As11 As21 2.3814(11) C102 C103 1.502(7) As11 As21 2.3814(11) C103 O12 1.427(5) As2 As21 0.893(4) C104 O12 1.434(6) As2 As1 2.383(5) C104 C101 1.504(7) As2 As2 2.428(6) C104 Cs1 3.874(5) As2 As3 2.456(3) Cs2 O22 3.455(4) As21 As1 1.662(3) Cs2 O22 3.455(4) As21 As21 2.4350(15) Cs2 O22 3.455(4) As21 As3 2.4657(8) Cs2 O22 3.455(4) As3 As2 2.456(3) Cs2 O22 3.455(4) As3 As2 2.456(3) Cs2 O22 3.455(4) As3 As21 2.4656(8) Cs2 O21 3.518(4) As3 As21 2.4657(8) Cs2 O21 3.518(4)

6 Table A-2: Selected Bond Lengths for [Cs2(18-crown-6)3][H(cbto)2]2·2Hcbto·2H2O

Atom 1 Atom 2 Bond Length Cs O(4) 3.636(5) Cs O(4a)* 3.416(5) Cs O(5) 3.393(5) Cs O(5a)* 3.636(5) Cs O(6) 3.546(5) Cs O(6a)* 3.442(5) Cs O(7) 3.152(7) Cs O(8) 3.397(7) Cs O(9) 3.182(7) Cs O(10) 3.220(7) Cs O(11) 3.413(8) Cs O(12) 3.227(7) S(1) C(3) 1.740(4) S(2) C(12) 1.741(5) S(3) C(21) 1.744(4) O(1) N(1) 1.305(5) O(2) N(4) 1.353(5) O(3) N(7) 2.399(5) N(1) C(1) 1.298(6) N(4) C(10) 1.290(6) N(7) C(19) 1.315(6) C(1) C(2) 1.422(7) C(10) C(12) 1.434(9) C(19) C(20) 1.413(7) C(1) C(3) 1.450(6) C(10) C(21) 1.449(7) C(19) C(21) 1.445(6) C(2) N(2) 1.134(6) C(11) N(5) 1.119(8) C(20) N(8) 1.143(6) C(3) N(3) 1.286(5) C(12) N(6) 1.291(6) C(21) N(9) 1.297(5)

7 Table A-3: Bond Lengths for Na2(18-crown-6)3][Ph4C5H1]2

Atom 1 Atom 2 Length C41 C46 1.394(5) O4 C67 1.423(4) C1 C5 1.403(4) C41 C42 1.405(5) C67 C68 1.469(5) C1 C2 1.404(4) C42 C43 1.389(5) C68 O5 1.424(4) C2 C3 1.421(4) C43 C44 1.372(7) O5 C69 1.421(4) C2 C11 1.473(4) C44 C45 1.373(7) C69 C70 1.454(5) C3 C4 1.426(4) C45 C46 1.392(5) C70 O6 1.417(4) C3 C21 1.477(4) Na1 O7 2.444(2) O6 C71 1.444(4) C4 C5 1.431(4) Na1 O6 2.517(2) C71 C72 1.492(6) C4 C31 1.465(4) Na1 O8 2.559(2) O7 C82 1.418(4) C5 C41 1.475(4) Na1 O3 2.571(2) O7 C81 1.427(4) C11 C12 1.397(4) Na1 O4 2.590(2) C81 C86 1.488(5) C11 C16 1.398(4) Na1 O2' 2.632(12) C82 C83 1.486(5) C12 C13 1.375(4) Na1 O1 2.675(3) O8 C84 1.419(4) C13 C14 1.382(5) Na1 O5 2.695(2) O8 C83 1.430(4) C14 C15 1.376(5) Na1 O2 2.794(11) C84 C85 1.500(4) C15 C16 1.384(5) O1 C72 1.390(5) O9 C86 1.416(4) C21 C22 1.398(4) O1 C61 1.422(6) O9 C85 1.419(4) C21 C26 1.399(4) C61 C62 1.36(2) C86 C81 1.488(5) C22 C23 1.379(4) C61 C62' 1.447(14) C91 C92 1.55(2) C23 C24 1.381(4) C62 O2 1.50(2) C91' C92 1.26(2) C24 C25 1.382(5) O2 C63 1.116(11) C92 C93 1.275(9) C25 C26 1.380(4) C62' O2' 1.20(2) C92 C93' 1.450(14) C31 C32 1.399(4) O2' C63 1.541(12) C93 C94 1.274(11) C31 C36 1.404(4) C63 C64 1.434(8) C94 C95 1.529(11) C32 C33 1.380(5) C64 O3 1.428(5) C93' C94' 1.31(2) C33 C34 1.391(6) O3 C65 1.429(4) C94' C95 1.367(11) C34 C35 1.375(6) C65 C66 1.493(5) C95 C96 1.186(14) C35 C36 1.373(5) C66 O4 1.421(4)

8 Table A-4: Bond Lengths for [Cs(benzo-18-crown-6)2]I3

Atom 1 Atom 2 Length Cs1 O10 3.241(4) Cs1 O10 3.241(4) Cs1 O4 3.256(2) Cs1 O4 3.256(2) Cs1 O13 3.273(3) Cs1 O13 3.273(3) Cs1 O7 3.290(3) Cs1 O7 3.290(3) Cs1 O16 3.303(3) Cs1 O16 3.303(3) Cs1 O1 3.361(3) Cs1 O1 3.361(3) I1 I2 2.8969(10) I1 I2 2.8969(10) O1 C22 1.370(4) O1 C2 1.427(4) C2 C3 1.491(5) C3 O4 1.417(4) O4 C5 1.423(4) C5 C6 1.495(6) C6 O7 1.413(5) O7 C8 1.420(5) C8 C9 1.419(9) C9 O10 1.083(8) O10 C11 1.395(7) C11 C12 1.470(9) C12 O13 1.430(7) O13 C14 1.402(7) C14 C15 1.477(8) C15 O16 1.442(5) O16 C17 1.371(6) C17 C18 1.383(6) C17 C22 1.419(5) C18 C19 1.381(8) C19 C20 1.365(8) C20 C21 1.405(6) C21 C22 1.377(6)

8 Table A-5: Bond Lengths for [Cs2(benzo-18-crown-6)3](I3)2

Atom 1 Atom 2 Length C120 C120 1.355(11) Cs1 O210 3.122(4) C120 C121 1.389(7) Cs1 O204 3.164(2) C121 C122 1.397(5) Cs1 O213 3.214(3) C122 C122 1.389(8) Cs1 O104 3.263(2) O201 C222 1.374(4) Cs1 O207 3.282(3) O201 C202 1.444(4) Cs1 O201 3.288(2) C202 C203 1.493(5) Cs1 O216 3.316(3) C203 O204 1.421(4) Cs1 O101 3.408(3) O204 C205 1.423(4) Cs1 O107 3.429(3) C205 C206 1.502(6) Cs1 O107 3.527(3) C206 O207 1.417(5) Cs1 O101 3.535(3) O207 C208 1.406(5) Cs1 O104 3.741(3) C208 C209 1.414(8) I1 I2 2.9048(4) C209 O210 1.189(7) I2 I3 2.9085(4) O210 C211 1.419(5) O101 C122 1.380(4) C211 C212 1.489(7) O101 C102 1.437(4) C212 O213 1.425(5) O101 Cs1 3.535(3) O213 C214 1.418(5) C102 C103 1.489(6) C214 C215 1.489(6) C103 O104 1.422(5) C215 O216 1.435(4) O104 C105 1.428(5) O216 C217 1.374(4) O104 Cs1 3.741(3) C217 C218 1.381(5) C105 C106 1.483(7) C217 C222 1.407(5) C106 O107 1.427(5) C218 C219 1.396(6) O107 C108 1.420(5) C219 C220 1.379(6) O107 Cs1 3.429(3) C220 C221 1.385(5) C108 C108 1.491(11) C221 C222 1.390(5)

APPENDIX B

Bond Angles of Presented Sandwiches

Table B-1: Bond Angles for [Cs3(18-crown-6)4]As11

Atom 1 Atom 2 Atom 3 Angle O12 Cs1 O22 74.24(9) O21 Cs1 O22 44.83(12) Cs2 O22 Cs1 74.60(8) O21 Cs1 O22 44.83(12) Cs1 O21 Cs2 78.84(9) O21 Cs1 O22 44.83(12) O11 Cs1 O22 80.15(9) O21 Cs1 O22 45.75(12) O11 Cs1 O22 80.15(9) O21 Cs1 O22 45.75(12) O11 Cs1 O22 80.15(9) O21 Cs1 O22 45.75(12) O22 Cs1 O22 81.70(10) O22 Cs2 O21 46.99(12) O22 Cs1 O22 81.70(10) O22 Cs2 O21 46.99(12) O22 Cs1 O22 81.70(10) O22 Cs2 O21 46.99(12) O11 Cs1 O21 82.07(10) O22 Cs2 O21 46.99(12) O11 Cs1 O21 82.07(10) O22 Cs2 O21 46.99(12) O11 Cs1 O21 82.07(10) O22 Cs2 O21 46.99(12) O21 Cs2 O21 82.61(10) O22 Cs2 O21 47.95(12) O21 Cs2 O21 82.61(10) O22 Cs2 O21 47.95(12) O21 Cs2 O21 82.61(10) O22 Cs2 O21 47.95(12) O21 Cs2 O21 82.61(10) O22 Cs2 O21 47.95(12) O21 Cs2 O21 82.61(10) O22 Cs2 O21 47.95(12) O21 Cs2 O21 82.61(10) O22 Cs2 O21 47.95(12) O21 Cs1 O21 85.34(10) O11 Cs1 O12 50.91(8) O21 Cs1 O21 85.34(10) O11 Cs1 O12 50.91(8) O21 Cs1 O21 85.34(10) O11 Cs1 O12 50.91(8) C204 O22 Cs1 87.2(3) O11 Cs1 O12 52.73(9) O22 Cs2 O22 87.74(9) O11 Cs1 O12 52.73(9) O22 Cs2 O22 87.74(9) O11 Cs1 O12 52.73(9) O22 Cs2 O22 87.74(9) O12 Cs1 O21 67.98(9) O22 Cs2 O22 87.74(9) O12 Cs1 O21 67.98(9) O22 Cs2 O22 87.75(9) O12 Cs1 O21 67.98(9) O22 Cs2 O22 87.75(9) O22 Cs2 O21 73.99(10) C102 C103 Cs1 88.4(3) O22 Cs2 O21 74.00(10) O11 Cs1 O11 88.41(9) O22 Cs2 O21 74.00(10) O11 Cs1 O11 88.41(9) O22 Cs2 O21 74.00(10) O11 Cs1 O11 88.41(9) O22 Cs2 O21 74.00(10) C101 C104 Cs1 88.6(3) O22 Cs2 O21 74.00(10) C202 O22 Cs1 89.7(3) O12 Cs1 O22 74.24(9) O22 Cs2 O22 92.25(9) O12 Cs1 O22 74.24(9) O22 Cs2 O22 92.25(9)

O22 Cs2 O22 92.26(9) O11 Cs1 O12 118.20(9) O22 Cs2 O22 92.26(9) C204 O22 Cs2 120.8(6) O22 Cs2 O22 92.26(9) C201 O21 Cs1 122.3(6) O22 Cs2 O22 92.26(9) C202 O22 Cs2 122.7(6) O21 Cs2 O21 97.39(10) C101 O11 Cs1 123.4(3) O21 Cs2 O21 97.39(10) C203 O21 Cs1 124.4(6) O21 Cs2 O21 97.39(10) C102 O11 Cs1 124.5(3) O21 Cs2 O21 97.39(10) O22 Cs2 O21 132.05(12) O21 Cs2 O21 97.39(10) O22 Cs2 O21 132.05(12) O21 Cs2 O21 97.39(10) O22 Cs2 O21 132.05(12) O21 Cs1 O22 100.55(10) O22 Cs2 O21 132.05(12) O21 Cs1 O22 100.55(10) O22 Cs2 O21 132.05(12) O21 Cs1 O22 100.55(10) O22 Cs2 O21 132.05(12) O12 Cs1 O22 102.19(10) O22 Cs2 O21 133.00(12) O12 Cs1 O22 102.19(10) O22 Cs2 O21 133.01(12) O12 Cs1 O22 102.19(10) O22 Cs2 O21 133.01(12) O12 Cs1 O12 102.94(7) O22 Cs2 O21 133.01(12) O12 Cs1 O12 102.94(7) O22 Cs2 O21 133.01(12) O12 Cs1 O12 102.94(7) O22 Cs2 O21 133.01(12) C201 O21 Cs2 103.8(4) O12 Cs1 O21 147.61(10) C203 O21 Cs2 105.0(4) O12 Cs1 O21 147.61(10) O22 Cs2 O21 106.00(10) O12 Cs1 O21 147.61(11) O22 Cs2 O21 106.00(10) O11 Cs1 O22 150.95(10) O22 Cs2 O21 106.00(10) O11 Cs1 O22 150.95(10) O22 Cs2 O21 106.00(10) O11 Cs1 O22 150.96(10) O22 Cs2 O21 106.00(10) O12 C103 Cs 151.7(2) O22 Cs2 O21 106.01(10) O12 C104 Cs 152.8(2) C104 O12 Cs1 106.4(3) O12 Cs1 O22 154.67(10) O11 Cs1 O21 107.41(10) O12 Cs1 O22 154.67(10) O11 Cs1 O21 107.41(10) O12 Cs1 O22 154.67(10) O11 Cs1 O21 107.41(10) O11 Cs1 O21 161.18(11) C103 O12 Cs1 107.9(3) O11 Cs1 O21 161.18(11) O12 Cs1 O21 109.37(11) O11 Cs1 O21 161.18(11) O12 Cs1 O21 109.37(11) O22 Cs2 O22 179.998(1) O12 Cs1 O21 109.37(11) O21 Cs2 O21 179.999(1) O11 Cs1 O22 117.59(10) O21 Cs2 O21 180.0(0) O11 Cs1 O22 117.59(10) O22 Cs2 O22 180.0(0) O11 Cs1 O22 117.59(10) O21 Cs2 O21 180.00(10) O11 Cs1 O12 118.20(9) O22 Cs2 O22 180.00(11) O11 Cs1 O12 118.20(9)

6 Table B-2: Bond Angles for [Cs2(18-crown-6)3][H(cbto)2]2·2Hcbto·2H2O

Atom Atom Atom Cs O(6) Cs(a)* 76.7(1) Angle 1 2 3 C(28) O(4) C(29) 115.0(6) O(4) Cs O(5) 46.5(1) C(30) O(5) C(31) 117.9(7) O(4) Cs O(6a)* 45.9(1) C(32) O(6) C(33) 117.7(7) O(4) Cs O(7) 74.9(2) C(3) S(1) C(9) 88.6(2) O(4) Cs O(9) 151.1(2) C(12) S(2) C(18) 88.4(2) O(5) Cs O(6) 47.2(1) C(21) S(3) C(27) 89.1(2) O(5) Cs O(8) 152.1(2) C(1) N(1) O(1) 113.9(4) O(5) Cs O(9) 157.7(2) C(10) N(4) O(2) 111.5(4) O(6) Cs O(7) 154.1(2) C(19) N(7) O(3) 113.0(4) O(7) Cs O(8) 51.6(2) C(1) C(2) N(2) 178.2(7) O(7) Cs O(12) 51.9(3) C(10) C(11) N(5) 178.3(7) O(8) Cs O(9) 49.6(2) C(19) C(20) N(8) 177.4(5) O(10) Cs O(11) 49.4(3) N(1) C(1) C(3) 117.1(4) Cs O(4) Cs(a)* 75.8(1) N(4) C(10) C(12) 120.1(5) Cs O(5) Cs(a)* 76.1(1) N(7) C(19) C(21) 116.5(4)

7 Table B-3: Bond Angles for Na2(18-crown-6)3][Ph4C5H1]2

Atom 1 Atom 2 Atom 3 Angle C46 C41 C5 120.4(3) C42 C41 C5 122.7(3) C5 C1 C2 109.6(2) C43 C42 C41 120.7(4) C1 C2 C3 107.6(2) C44 C43 C42 121.0(4) C1 C2 C11 123.2(2) C43 C44 C45 119.7(4) C3 C2 C11 129.1(2) C44 C45 C46 119.8(4) C2 C3 C4 107.9(2) C45 C46 C41 122.0(4) C2 C3 C21 126.8(2) O7 Na1 O6 82.32(8) C4 C3 C21 125.3(2) O7 Na1 O8 66.82(7) C3 C4 C5 107.5(2) O6 Na1 O8 86.05(8) C3 C4 C31 125.6(3) O7 Na1 O3 90.06(8) C5 C4 C31 126.9(2) O6 Na1 O3 172.38(9) C1 C5 C4 107.4(2) O8 Na1 O3 90.87(8) C1 C5 C41 122.3(3) O7 Na1 O4 138.63(8) C4 C5 C41 130.0(3) O6 Na1 O4 120.80(9) C12 C11 C16 116.6(3) O8 Na1 O4 80.21(8) C12 C11 C2 120.0(3) O3 Na1 O4 65.34(8) C16 C11 C2 123.4(3) O7 Na1 O2' 109.9(3) C13 C12 C11 122.1(3) O6 Na1 O2' 119.8(2) C12 C13 C14 120.2(3) O8 Na1 O2' 153.9(2) C15 C14 C13 119.0(3) O3 Na1 O2' 63.0(2) C14 C15 C16 120.7(3) O4 Na1 O2' 88.7(3) C15 C16 C11 121.3(3) O7 Na1 O1 77.54(9) C22 C21 C26 116.5(3) O6 Na1 O1 64.20(9) C22 C21 C3 121.5(2) O8 Na1 O1 136.28(9) C26 C21 C3 122.0(3) O3 Na1 O1 114.33(9) C23 C22 C21 121.9(3) O4 Na1 O1 141.98(9) C22 C23 C24 120.6(3) O2' Na1 O1 62.0(3) C23 C24 C25 118.6(3) O7 Na1 O5 142.52(9) C26 C25 C24 120.8(3) O6 Na1 O5 62.94(7) C25 C26 C21 121.6(3) O8 Na1 O5 95.60(8) C32 C31 C36 116.8(3) O3 Na1 O5 124.38(8) C32 C31 C4 121.9(3) O4 Na1 O5 61.62(7) C36 C31 C4 121.3(3) O2' Na1 O5 99.8(2) C33 C32 C31 121.6(3) O1 Na1 O5 97.90(9) C32 C33 C34 120.0(4) O7 Na1 O2 93.0(2) C35 C34 C33 119.3(3) O6 Na1 O2 122.1(2) C36 C35 C34 120.6(3) O8 Na1 O2 143.9(3) C35 C36 C31 121.6(3) O3 Na1 O2 58.2(2) C46 C41 C42 116.8(3)

O4 Na1 O2 100.1(2) C69 O5 Na1 110.0(2) O1 Na1 O2 58.5(2) C68 O5 Na1 116.7(2) O5 Na1 O2 116.5(2) O5 C69 C70 109.0(3) C72 O1 C61 115.4(4) O6 C70 C69 108.9(3) C72 O1 Na1 116.7(3) C70 O6 C71 111.3(3) C61 O1 Na1 116.7(3) C70 O6 Na1 120.3(2) C62 C61 O1 110.1(9) C71 O6 Na1 111.6(2) O1 C61 C62' 113.9(7) O6 C71 C72 111.8(3) C61 C62 O2 106.8(12) O1 C72 C71 107.2(3) C63 O2 C62 120.3(11) C82 O7 C81 113.3(2) C63 O2 Na1 120.4(8) C82 O7 Na1 117.0(2) C62 O2 Na1 116.7(8) C81 O7 Na1 125.4(2) O2' C62' C61 123.6(12) O7 C81 C86 114.0(3) C62' O2' C63 112.1(12) O7 C82 C83 108.5(2) C62' O2' Na1 119.0(10) C84 O8 C83 113.7(2) C63 O2' Na1 111.0(5) C84 O8 Na1 120.4(2) O2 C63 C64 121.7(8) C83 O8 Na1 104.5(2) C64 C63 O2' 105.2(7) O8 C83 C82 107.2(3) O3 C64 C63 110.6(4) O8 C84 C85 113.0(3) C64 O3 C65 112.7(3) C86 O9 C85 111.2(3) C64 O3 Na1 119.8(3) O9 C85 C84 109.4(3) C65 O3 Na1 106.7(2) O9 C86 C81 111.5(3) O3 C65 C66 112.1(3) C91' C92 C93' 102.4(13) O4 C66 C65 106.8(3) C93 C92 C91 109.8(9) C66 O4 C67 113.4(3) C94 C93 C92 114.3(8) C66 O4 Na1 117.5(2) C93 C94 C95 110.2(7) C67 O4 Na1 116.2(2) C94' C93' C92 110.0(10) O4 C67 C68 108.3(3) C93' C94' C95 105.7(10) O5 C68 C67 108.4(3) C96 C95 C94' 131.1(12) C69 O5 C68 110.8(3) C96 C95 C94 100.3(10)

8 Table B-4: Bond Angles for [Cs(benzo-18-crown-6)2]I3

Atom 1 Atom 2 Atom 3 Angle O13 Cs1 O16 148.96(9) O10 Cs1 O10 74.0(3) O7 Cs1 O16 108.39(8) O10 Cs1 O4 101.56(9) O7 Cs1 O16 113.03(7) O10 Cs1 O4 99.16(10) O10 Cs1 O16 160.45(12) O10 Cs1 O4 99.16(10) O10 Cs1 O16 92.87(16) O10 Cs1 O4 101.56(9) O4 Cs1 O16 94.67(6) O4 Cs1 O4 153.99(9) O4 Cs1 O16 68.84(6) O10 Cs1 O13 50.53(13) O13 Cs1 O16 148.96(9) O10 Cs1 O13 110.26(14) O13 Cs1 O16 50.82(9) O4 Cs1 O13 62.26(7) O7 Cs1 O16 113.03(7) O4 Cs1 O13 123.16(7) O7 Cs1 O16 108.39(8) O10 Cs1 O13 110.26(14) O16 Cs1 O16 103.20(11) O10 Cs1 O13 50.53(13) O10 Cs1 O1 152.26(8) O4 Cs1 O13 123.16(7) O10 Cs1 O1 109.20(16) O4 Cs1 O13 62.26(7) O4 Cs1 O1 50.80(6) O13 Cs1 O13 159.12(14) O4 Cs1 O1 106.86(6) O10 Cs1 O7 50.09(9) O13 Cs1 O1 105.32(8) O10 Cs1 O7 74.50(14) O13 Cs1 O1 90.64(7) O4 Cs1 O7 151.65(7) O7 Cs1 O1 157.53(7) O4 Cs1 O7 51.39(7) O7 Cs1 O1 86.58(7) O13 Cs1 O7 93.48(8) O16 Cs1 O1 75.83(7) O13 Cs1 O7 74.52(8) O16 Cs1 O1 45.65(6) O10 Cs1 O7 74.50(14) O10 Cs1 O1 109.20(15) O10 Cs1 O7 50.09(9) O10 Cs1 O1 152.26(8) O4 Cs1 O7 51.39(7) O4 Cs1 O1 106.86(6) O4 Cs1 O7 151.65(7) O4 Cs1 O1 50.80(6) O13 Cs1 O7 74.52(8) O13 Cs1 O1 90.64(7) O13 Cs1 O7 93.48(8) O13 Cs1 O1 105.32(8) O7 Cs1 O7 110.66(12) O7 Cs1 O1 86.58(7) O10 Cs1 O16 92.87(16) O7 Cs1 O1 157.53(7) O10 Cs1 O16 160.45(11) O16 Cs1 O1 45.65(6) O4 Cs1 O16 68.84(6) O16 Cs1 O1 75.83(7) O4 Cs1 O16 94.67(6) O1 Cs1 O1 81.11(9) O13 Cs1 O16 50.82(9)

8 Table B-5: Bond Angles for [Cs2(benzo-18-crown-6)3](I3)2

Atom 1 Atom 2 Atom 3 Angle O201 Cs1 O107 107.81(6) O210 Cs1 O204 99.34(9) O216 Cs1 O107 148.30(7) O210 Cs1 O213 54.02(10) O101 Cs1 O107 107.18(6) O204 Cs1 O213 124.75(7) O210 Cs1 O107 80.22(12) O210 Cs1 O104 74.07(10) O204 Cs1 O107 104.90(6) O204 Cs1 O104 152.97(6) O213 Cs1 O107 114.30(7) O213 Cs1 O104 73.11(7) O104 Cs1 O107 48.49(7) O210 Cs1 O207 49.93(9) O207 Cs1 O107 81.33(8) O204 Cs1 O207 51.80(7) O201 Cs1 O107 155.03(6) O213 Cs1 O207 96.78(8) O216 Cs1 O107 158.45(6) O104 Cs1 O207 110.82(8) O101 Cs1 O107 87.49(6) O210 Cs1 O201 110.72(11) O107 Cs1 O107 47.69(9) O204 Cs1 O201 52.23(6) O210 Cs1 O101 154.43(8) O213 Cs1 O201 89.55(6) O204 Cs1 O101 104.40(6) O104 Cs1 O201 154.77(6) O213 Cs1 O101 103.46(7) O207 Cs1 O201 88.91(7) O104 Cs1 O101 88.51(6) O210 Cs1 O216 96.37(11) O207 Cs1 O101 155.46(7) O204 Cs1 O216 96.65(6) O201 Cs1 O101 77.64(6) O213 Cs1 O216 50.16(6) O216 Cs1 O101 71.77(6) O104 Cs1 O216 110.03(6) O101 Cs1 O101 44.10(8) O207 Cs1 O216 112.86(8) O107 Cs1 O101 87.04(7) O201 Cs1 O216 45.68(6) O107 Cs1 O101 102.36(6) O210 Cs1 O101 111.44(8) O210 Cs1 O104 157.19(10) O204 Cs1 O101 148.45(6) O204 Cs1 O104 70.09(6) O213 Cs1 O101 72.33(7) O213 Cs1 O104 148.57(7) O104 Cs1 O101 50.03(6) O104 Cs1 O104 105.82(5) O207 Cs1 O101 159.60(7) O207 Cs1 O104 112.17(7) O201 Cs1 O101 107.77(6) O201 Cs1 O104 79.40(6) O216 Cs1 O101 73.86(6) O216 Cs1 O104 104.75(6) O210 Cs1 O107 111.71(11) O101 Cs1 O104 83.11(6) O204 Cs1 O107 65.42(6) O107 Cs1 O104 45.70(6) O213 Cs1 O107 161.44(7) O107 Cs1 O104 83.10(6) O104 Cs1 O107 92.20(7) O101 Cs1 O104 45.57(6) O207 Cs1 O107 77.56(8)

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