Chemical crystallography chemistry research and applications

CHEMISTRY RESEARCH AND APPLICATIONS CHEMICAL CRYSTALLOGRAPHY No part of this digital document may be reproduced, stored in a retrieval system or transmitted in any form or by any means The publisher has taken reasonable care in the preparation of this digital document, but makes no expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions No liability is assumed for incidental or consequential damages in connection with or arising out of information contained herein This digital document is sold with the clear understanding that the publisher is not engaged in rendering legal, medical or any other professional services CHEMISTRY RESEARCH AND APPLICATIONS Additional books in this series can be found on Nova‘s website at: https://www.novapublishers.com/catalog/index.php?cPath=23_29&seriesp= Chemistry%20Research%20and%20Applications&sort=2a&page=1 Additional e-books in this series can be found on Nova‘s website at: https://www.novapublishers.com/catalog/index.php?cPath=23_29&seriespe= Chemistry+Research+and+Applications CHEMISTRY RESEARCH AND APPLICATIONS CHEMICAL CRYSTALLOGRAPHY BRYAN L CONNELLY EDITOR Nova Science Publishers, Inc New York Copyright © 2010 by Nova Science Publishers, Inc All rights reserved No part of this book may be reproduced, stored in a retrieval system or transmitted in any form or by any means: electronic, electrostatic, magnetic, tape, mechanical photocopying, recording or otherwise without the written permission of the Publisher For permission to use material from this book please contact us: Telephone 631-231-7269; Fax 631-231-8175 Web Site: http://www.novapublishers.com NOTICE TO THE READER The Publisher has taken reasonable care in the preparation of this book, but makes no expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions No liability is assumed for incidental or consequential damages in connection with or arising out of information contained in this book The Publisher shall not be liable for any special, consequential, or exemplary damages resulting, in whole or in part, from the readers‘ use of, or reliance upon, this material Any parts of this book based on government reports are so indicated and copyright is claimed for those parts to the extent applicable to compilations of such works Independent verification should be sought for any data, advice or recommendations contained in this book In addition, no responsibility is assumed by the publisher for any injury and/or damage to persons or property arising from any methods, products, instructions, ideas or otherwise contained in this publication This publication is designed to provide accurate and authoritative information with regard to the subject matter covered herein It is sold with the clear understanding that the Publisher is not engaged in rendering legal or any other professional services If legal or any other expert assistance is required, the services of a competent person should be sought FROM A DECLARATION OF PARTICIPANTS JOINTLY ADOPTED BY A COMMITTEE OF THE AMERICAN BAR ASSOCIATION AND A COMMITTEE OF PUBLISHERS LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA Chemical crystallography / editor, Bryan L Connelly p cm ISBN 978-1-61668-513-3 (eBook) Crystallography I Connelly, Bryan L QD905.2.C44 2009 548'.3 dc22 2010002300 Published by Nova Science Publishers, Inc  New York CONTENTS Preface Chapter Chapter Chapter Chapter Chapter Index vii Dipicolinic Acid, Its Analogues, and Derivatives: Aspects of Their Coordination Chemistry Alvin A Holder, Lesley C Lewis-Alleyne, Don vanDerveer, and Marvadeen Singh-Wilmot Synthesis and Structural Characterization of ThiopheneFunctionalized Metal Dithiolenes Seth C Rasmussen and Chad M Amb Crystal Chemistry of an Atropisomer: Conformation, Chirality, Aromaticity and Intermolecular Interactions of Diphenylguanidine Manuela Ramos Silva, Pedro S Pereira Silva, Ana Matos Beja and José António Paixão Construction and Structure of Metal-Organic Frameworks with Specific Ion-Exchange Property Man-Sheng Chen, Zhi Su, Shui-Sheng Chen and Wei-Yin Sun Substituent Effect on the Structures of Zinc 1,4Benzenedicarboxylate Coordination Polymers Synthesized in Dimethyl Sulfoxide Shi-Yao Yang and Xiao-Bin Xu 69 103 131 153 161 PREFACE Chemical crystallography is the study of the principles of chemistry behind crystals and their use in describing structure-property relations in solids The principles that govern the assembly of crystal and glass structures are described, models of many of the technologically important crystal structures are studied, and the effect of crystal structure on the various fundamental mechanisms responsible for many physical properties are discussed This new book presents and reviews data on the coordination chemistry of several metal complexes with dipicolinic acid and the crystal structure of some antimalarial metal complexes Chapter 1-2,6-Pyridinedicarboxylic acid (dipicolinic acid) is a widely used building block in coordination and supramolecular chemistry The crystal structure of dipicolinic acid was first solved in 1973, which confirmed its molecular formula of C7H5NO4, a molar mass of 167.119 g mol-1, and the resulting composition of its constituent atoms (C, 50.31%; H, 3.02%; N, 8.38%; and O, 38.29%) Dipicolinic acid and its analogues are known to form many intriguing complexes with main group and other metal ions from as far back as 1877 The corresponding bis-acid (DPA), bis-ester (DPE), and bis-amide (DPAM) derivatives behave as tridentate ligands, which efficiently coordinate to various metal ions This chapter will discuss the coordination chemistry of several metal complexes with dipicolinic acid, its analogues, and derivatives as ligands Chapter 2- Transition metal dithiolenes are versatile complexes capable of a wide range of oxidation states, coordination geometries, and magnetic moments.1 As a consequence, these complexes have been widely studied as building blocks for crystalline molecular materials Particularly successful are the square-planar metal dithiolenes (Chart 1), from which materials have been produced that exhibit conducting, magnetic, and nonlinear optical properties, as well as superconductivity in some cases.1-3 In their application to molecular- based viii Bryan L Connelly conductors, metal dithiolenes can play several different roles Metal dithiolenes may form an effective conduction pathway through intermolecular face-to-face stacking, or can play a supportive role as counterions to other planar molecules (such as perylene or tetrathiafulvalene derivatives, Chart 1) which provide the actual conduction path.3 When acting as counterions, such dithiolene complexes can additionally impart magnetic properties to the molecular conductors via interactions between localized spins of the metal dithiolene with the intinerant spins of conduction electrons As a result of such research efforts, there now exists a variety of available dithiolene ligands which have been applied to produce a broad range of metal dithiolene materials One focus of study has been the use of electronically delocalized dithiolene ligands to explore the influence on the solid-state structures and the resulting material properties.2 Of particular interest has been the preparation and study of metal dithiolenes functionalized with thiophene moieties The application of such extended -systems and sulfur-rich ligands are expected to enhance solid-state interactions, which could result in enhanced electrical conductivity or higher magnetic transition temperatures As the molecular packing in the crystal is determined by the total balance of many weak intermolecular interactions, and S···S/M···S forces (hydrogen bonding, van der Waals, interactions),2,3 the additional thiophene content would increase such intermolecular interactions and provide more significant overlap of frontier orbitals In addition, such complexes could provide potential precursors to metaldithiolene-containing conjugated polymers Chapter 3- This paper reviews the crystal chemistry of 25 diphenylguanidine/diphenylguanidinium compounds Diphenylguanidine is an atropisomer and several conformations have been isolated in the solid state Such conformations are investigated and the conformation description, chirality, aromaticity of the flexible molecule are systematized in this paper The dipolar moment and octupolar character are probed Intermolecular interactions are classified Two new salts are reported: N,N‘-Diphenylguanidinium nicotinate hydrate and N,N‘-Diphenylguanidinium 5-nitrouracilate dihydrate The former crystallizes in a chiral space group, with the phenyl rings of the cation oriented like the blades of a propeller The latter crystallizes in the centrosymmetric, triclinic space group P-1, and the cation exhibits and anti-anti conformation Keywords: atropisomer; polarizability; X-ray diffraction Chapter 4- Remarkable progress has been achieved in the area of metalorganic frameworks (MOFs) in recent years not only due to their diverse topology and intriguing structures but also owing to their interesting physical and chemical properties MOFs with specific ion exchange property have attracted great Preface ix attention for their potential application in molecular/ionic recognition and selective guest inclusion Despite the difficulty in predicting the structure and property of MOFs, the increasing knowledge regarding the synthesis methods and characterization techniques has largely expanded for the rational designs In this chapter the recent works in cation/anion exchange with zero- (0D), one- (1D), two- (2D) and three-dimensional (3D) frameworks from our and other groups will be highlighted Cation exchange mainly concentrates on the metal ions and organic cations such as Mm+, [M(H2O)n]m+, [Me2NH2]+, etc., while anion exchange comprises the majority of the counteranions, e.g., ClO4-, NO3-, BF4-, and so on The functions of the exchanged compounds, i.e., enhancement of gas adsorption and photoluminescence, were greatly reformed Chapter 5- The coordination polymer [Zn(tmbdc)(dmso)2]·2(DMSO) (tmbdc = 2,3,5,6-tetramethyl-1,4-benzenedicarboxylate) has been synthesized by layer diffusion in DMSO (dimethyl sulfoxide) solution The compound contains 1D chain formed by octahedraly coordinated Zn2+ ion chelated by the carboxyl groups of tmbdc In another recently reported coordination polymer [Zn2(bdc)2(dmso)2]·5(DMSO) (bdc = 1,4-benzenedicarboxylate) prepared under the same condition, pairs of Zn2+ ions are bridged by four carboxyl groups to form paddle-wheel sub unit and the 2D (4,4) net structure Analysis of the structures reveals that the substituents of the ligands determine the coordination environments of zinc ions and the coordination modes of the carboxyls, and thus the final structures of the coordination polymers In: Chemical Crystallography ISBN: 978-1-60876-281-1 Editors: Bryan L Connelly, pp 153-159 © 2010 Nova Science Publishers, Inc Chapter SUBSTITUENT EFFECT ON THE STRUCTURES OF ZINC 1,4-BENZENEDICARBOXYLATE COORDINATION POLYMERS SYNTHESIZED IN DIMETHYL SULFOXIDE Shi-Yao Yang* and Xiao-Bin Xu College of Chemistry and Chemical engineering, Xiamen University, Xiamen, 361005, China ABSTRACT The coordination polymer [Zn(tmbdc)(dmso)2]·2(DMSO) (tmbdc = 2,3,5,6-tetramethyl-1,4-benzenedicarboxylate) has been synthesized by layer diffusion in DMSO (dimethyl sulfoxide) solution The compound contains 1D chain formed by octahedraly coordinated Zn2+ ion chelated by the carboxyl groups of tmbdc In another recently reported coordination polymer [Zn2(bdc)2(dmso)2]·5(DMSO) (bdc = 1,4benzenedicarboxylate) prepared under the same condition, pairs of Zn2+ ions are bridged by four carboxyl groups to form paddle-wheel sub unit and the 2D (4,4) net structure Analysis of the structures reveals that the substituents of the ligands determine the coordination environments of zinc ions and the coordination modes of the carboxyls, and thus the final structures of the coordination polymers * Corresponding author: Email: syyang@xmu.edu.cn 154 Shi-Yao Yang and Xiao-Bin Xu INTRODUCTION The properties and potential applications of coordination polymers (CPs) are closely related to their structures, therefore the rational design and synthesis of CPs is one of the most important and urgent task of crystal engineering [1-4] However, it is still a great challenge to synthesize a structure by design because there are numerous influences such as the substituents on ligands, solvents, synthetic temperatures, etc, that can have decisive roles in determining of the structure and crystal packing [4-13] These uncertainties can be reduced by the use of well designed ligands that bind metal ions at chelating sites, such as carboxylates linkers that have the ability to aggregate metal ions into secondary building units (SBUs) Among the organic ligands used in the assembly of coordination polymers, benzene polycarboxylate species have been extensively explored to produce robust crystalline materials due to their versatile coordination ability [1,4] Some analogous compounds possessing substituents, such as aryl, nitro or hydroxyl groups, may provide new chance to rationally modulate and control the network structures and new understanding of crystal engineering In particular, when there are different substituents on ligands, the coordination environments of metal ions can be changed, and the structures with completely different topologies are obtained [5-9] The influence of the four methyl groups of H2tmbdc (2,3,5,6-tetramethyl1,4-benzenedicarboxylic acid) on the assembly of CPs in DMF (N,Ndimethylformamide) has been investigated In the work of Yaghi‘s group, they found that the square grid structure constructed from paddle-wheel units of Zn2+ could not be formed with tmbdc in MOF-47 because of the sterically demanding They claimed that the dihedral angle ( , Scheme 1) between the planes of benzene and carboxyl groups play a determining role in the formation of the paddle-wheel motif The value for MOF-47 was 84 , and a tetrahedral SBU and therefore a double layer motif of the structure was formed [5] Nevertheless, in the work of Kim‘s group, the substituents did not show influence on the formation of the paddle-wheel structure in [Zn2(1,4bdc)(tmbdc)(dabco)] ( = 75.0(1)°), and [Zn2(tmbdc)2(dabco)] ( = 73.9(1)°) (dabco = 4-diazabicyclo[2.2.2]octane) [4] The contradiction shows that other factors may also play the decisive roles In many cases, it is difficult to predict which factor will be the dominant one The true engineering of crystal structures is still a distant aim which demands more extensive and intensive investigations Substituent Effect on the Structures of Zinc 1,4-Benzenedicarboxylate…155 Scheme Definition of the dihedral angle, , between carboxyl and benzene ring Among the other factors, the effect of solvent on the assembly of CPs is apparent The solvents, in many cases act as ancillary ligands, can compete with the ligands The coordination environment adopted by the metal centre, and therefore the structure of the coordination polymer, can be very variable and unpredictable [10-13] DMF and DMSO (dimethyl sulfoxide) are among the solvents that have great tendencies to be included in organic crystals via multi-point recognition between solvent and solute [14] DMF has been largely used in the syntheses of CPs, especially for highly porous structures, while DMSO is much less explored According to CCDC search, [15] there are 56 zinc benzenecarboxylate CPs which have been synthesized with DMF as solvent, and for DMSO, the number is 11 In particular, for zinc 1,4benzenedicarboxylates, the number for DMF is 21, and for DMSO, only 3: [Zn4(OH)(bdc)3(dmso)4] 2H2O [16,17], [Zn2(bdc)2(dmso)2] 5DMSO [18], and (Bu4N)[Zn(bdc)1.5(dmso)] 0.67DMSO 0.25pz (pz = pyrazine) [19] We have synthesized and characterized the zinc 1,4-benzenedicarboxylate coordination polymer [Zn2(bdc)2(dmso)2] 5DMSO by layer diffusion in DMSO [18] In 1, pairs of Zn2+ ions are bridged by four carboxyl groups to form paddle-wheel SBU (Fig a) The SBUs are further extended by bdc and result in the formation of the 2D (4,4) net The 2D nets pack along the a axis forming 1D channels occupied by large amount of solvent DMSO molecules (Fig a) The ratio of solvent molecules to Zn2+ ions is 2.5, which is much higher than 0~1 for similar structures synthesized in DMF or analog solvents [3,10,13] In order to explore the substituent effect on the assembly of coordination polymers, the influence of other factors should be excluded Therefore the same synthetic condition as that for was applied to synthesize the zinc 2,3,5,6-tetramethyl-1,4-benzenedicarboxylate, [Zn(tmbdc)(dmso)2]·2(DMSO) 2, except that H2bdc was replaced by H2tmbdc [20] 156 Shi-Yao Yang and Xiao-Bin Xu RESULT AND DISCUSSION X-ray structure determination [21] reveals that there are one Zn2+ ion, one tmbdc dianion and four DMSO molecules in the asymmetric unit in The Zn2+ ion is in a severely distorted octahedral geometry, coordinated by two carboxyl groups in chelate mode and two DMSO molecules (Fig b) Due to the steric hindrance of the four methyl groups, the angle in is 85.4° This value is even larger than 84 in MOF-47, [5] and the paddle-wheel SBU is not adopted by 2, either The orientations of the two tmbdc dianions coordinated to the same Zn2+ ion are at an angle of 134.5°, therefore a 1D chain is formed (Fig b) By comparison with 2, the average in is 10.55 (23.0, 7.5, 3.5 and 8.2° for four crystallographically independent carboxyl groups, all are smaller than 25° in Zn(ABDC)(DMF)·(C6H5Cl)0.25 (MOF-46, ABDC = 2-amino-1,4benzenedicarboxylate) [5]) The methyl groups play a determining role in the formation of the mononuclear metal center and thus the 1D structure of There are also DMSO solvent molecules included in the crystal structure of It is worth noticing that the ratio of solvent DMSO molecules to Zn2+ ions is 2, which is unexpected high for closely packed 1D chain structure The result again shows the strong tendency of DMSO to be included in the structures of coordination polymers Compared to DMF, DMSO also has a stronger tendency to coordinate to Zn2+ ion Figure.1 The coordination environments of Zn2+ ions in (a) and (b) Hydrogen atoms and solvent DMSO molecules are omitted for clarity Selected bond lengths (Å) and angles ( ) for 2: Zn1 O1 2.043(3), Zn1 O2 2.346(3), Zn1 O3 2.022(3), O1 Zn1 O2 58.68(12), O1 Zn1 O3 102.62(14), O1 Zn1 O1A 156.9(2), O1 Zn1 O2A 104.12(13), O1 Zn1 O3A 91.85(13), O2 Zn1 O3 89.84(14), O2 Zn1 O2A 92.79(18), O2 Zn1 O3A 150.14(12), O3 Zn1 O3A 102.4(2) Symmetry code: A x 1, y, z 3/2 Substituent Effect on the Structures of Zinc 1,4-Benzenedicarboxylate…157 Figure Views of the structures of (a) and (b) The coordination polymers are shown in ball and stick mode, zinc ions are shown in polyhedra, DMSO solvent molecules are shown in CPK mode CONCLUSIONS In conclusion, 1D coordination polymer [Zn(tmbdc)(dmso)2]·2(DMSO) has been synthesized with 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid in DMSO The structure contains 1D chains formed by octahedraly coordinated Zn2+ ions chelated by the carboxyl groups of tmbdc, rather than the 2D (4,4) nets constructed from paddle-wheel SBU of pairs Zn2+ ions as found in [Zn2(bdc)2(dmso)2] 5DMSO Analysis of the structure reveals that the steric hindrance of the four methyl groups of tmbdc determines the coordination environments of the zinc ions and the coordination modes of the carboxyls, and thus the final structures of the coordination polymers The result also shows that DMSO is a stronger ancillary ligand and is also easier to be included in the structures of coordination polymers, compared to DMF DMSO can be a better solvent for the syntheses of porous coordination polymers ACKNOWLEDGMENT We thank the National Natural Science Foundation of China (20471049) for financial assistance 158 Shi-Yao Yang and Xiao-Bin Xu REFERENCES [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] Eddaoudi, M; Kim, J; Rosi, N; Vodak, D; Wachter, J; O‘Keeffe, M; Yaghi, O M Science, 2002, 295, 469-472 Rowsell, JLC; Millward, AR; Park, KS; Yaghi, OM J Am Chem Soc., 2004, 126, 5666-5667 Li, H; Eddaoudi, M; Groy, TL; Yaghi, OM J Am Chem Soc., 1998, 120, 8571-8572 Chun, H; Dybtsev, DN; Kim, H; Kim, K Chem Eur J, 2005, 11, 35213529 Braun, ME; Steffek, CD; Kim, J; Rasmussen, PG; Yaghi, OM Chem Commun, 2001, 2532-2533 Li, XJ; Cao, R; Guo, ZG; Li, YF; Zhu, XD Polyhedron, 2007, 26, 39113919 Du, M; Zhang, ZH; You, YP; Zhao, XJ CrystEngComm, 2008, 10, 306321 Ren, H; Song, TY; Xu, JN; Jing, SB; Yu, Y; Zhang, P; Zhang, LR Cryst Growth Des., 2009, 9, 105-112 Ma, LF; Wang, LY ; Wang, YY; Du, M; Wang, JG CrystEngComm, 2009, 11, 109-117 Edgar, M; Mitchell, R; Slawin, AMZ; Lightfoot, P; Wright, PA Chem Eur J, 2001, 7, 5168-5175 Hawxwell, SM; Adams, H; Brammer, L Acta Cryst, 2006, B62, 808814 Burrows, AD; Cassar, K; Friend, RMW; Mahon, MF; Rigby, SP; Warren, JE CrystEngComm, 2005, 7, 548-550 Wang, FK; Yang, SY; Huang, RB; Zheng, LS; Batten, SR CrystEngComm, 2008, 10, 1211-1215 Nangia, A; Desiraju, GR Chem Commun, 1999, 605-606 Cambridge Structural Database; Version 5.30, update Feb 2009, see also Allen, FH Acta Cryst, 2002, B58, 380-388 Wang, R; Hong, M; Liang, Y; Cao, R Acta Cryst, 2001, E57, m277m279 Zevaco, TA; Männle, D; Walter, O; Dinjus, E Appl Organometal Chem., 2007, 21, 970-977 Yang, SY; Long, LS; Huang, RB; Zheng, LS; Ng, SW Acta Cryst, 2005, E61, m1671-m1673 Yang, SY; Du, C; Huang, RB; Ng, SW Acta Cryst, 2007, E63, m2788 Substituent Effect on the Structures of Zinc 1,4-Benzenedicarboxylate…159 [20] Synthesis of 2: Zinc nitrate hexahydrate (0.059 g, 0.20 mmol) in DMSO (2 ml) was placed in a 0.5 mm 15 mm test tube, and then 2,3,5,6tertbutyl-1,4-benzenedicarboxylic acid (0.052 g, 0.20 mmol) in DMSO (2 ml) was carefully put on top of it, finally, tributylamine (0.20 ml) was added on the top The tube was covered and set aside for five days Colorless needle-shaped crystals (0.066g, yield 55%) formed on the wall of the tube Elemental analysis, C20H36O8S4Zn: found (calc.) C 40.61 (40.13), H 5.88 (6.02), S 21.17 (21.44)% [21] Crystal data for [Zn(tmbdc)(dmso)2] 2DMSO: Formula C20H36O8S4Zn, M = 598.10, monoclinic, space group C2/c, a = 12.1980(9), b = 12.9463(10), c = 17.8471(13) Å, = 102.705(1)°, V = 2749.4(4) Å3, Z = 4, Dc = 1.445 Mg/m3, = 1.237 mm-1, T = 223(2) K, Rint = 0.0302, full-matrix least-squares refinement on F2, R1 = 0.0687, wR2 = 0.1820, = 0.874, 0.610 e Å INDEX A absorption spectra, 98 accelerator, 104 access, 95, 138 accounting, 22 acetone, 71, 91 acetonitrile, 48, 71, 83, 90, 97, 144 acid, vii, 1, 2, 4, 5, 6, 7, 8, 10, 13, 26, 31, 32, 35, 39, 43, 47, 48, 51, 53, 54, 59, 106, 107, 115, 116, 145, 146, 154, 157, 159 adsorption, ix, 98, 132, 146 AFM, 148 alkaline earth metals, ammonium, ammonium salts, antipsychotic, 104 antipsychotic drugs, 104 applications, 94, 99, 104, 132, 142, 154 aqueous solutions, 105 arginine, 104 argon, 86 aromatic rings, 41, 49, 111 aspartate, 104 asymmetry, 9, 14, 17, 20, 72 atomic force, 148 authors, 96, 97 B band gap, 96, 98 basicity, 45 behavior, 4, 49, 58, 77, 83, 86, 95, 96, 97, 98, 134, 142 benzene, 134, 139, 144, 154, 155 binding, 20, 132 bonding, viii, 2, 14, 15, 16, 17, 20, 22, 25, 26, 27, 31, 32, 33, 36, 37, 38, 39, 50, 51, 52, 53, 56, 58, 70, 122, 136, 144, 148 bonds, 5, 7, 9, 12, 13, 14, 18, 19, 20, 22, 25, 33, 36, 41, 42, 43, 44, 47, 52, 57, 88, 92, 105, 110, 115, 118, 121, 122, 123, 125 building blocks, vii, 69, 70, 148 C Ca2+, 54, 145 cadmium, 51, 144 carbon, 92, 96, 115 carbon atoms, 115 carboxylic groups, 3, 17, 44 catalysis, 139, 142 cation, viii, ix, 9, 14, 16, 18, 27, 28, 39, 40, 44, 52, 56, 57, 75, 76, 77, 81, 82, 83, 90, 103, 105, 106, 111, 112, 118, 121, 132, 133, 138, 145, 146, 148 C-C, 22, 108 162 Index cell, 10, 13, 25, 27, 34, 56, 73, 104, 107, 108, 111, 115, 116, 117, 137 cell death, 104 cesium, 58 challenges, 94 channels, 143, 144, 145, 146, 155 character, viii, 11, 25, 33, 38, 103, 108, 125, 128 chelates, 10, 54 chemical properties, viii, 131 chemical reactions, 139 chirality, viii, 103, 106 chlorine, 31 chromium, 27 clarity, 109, 122, 137, 156 cleavage, clusters, 45 C-N, 52, 105, 109, 125, 126 CO2, cobalt, 35, 37 cohesion, 57, 110, 121 communication, 83 components, 28, 96 composition, vii, 1, compounds, viii, ix, 44, 54, 77, 103, 104, 106, 111, 115, 117, 121, 128, 132, 134, 136, 140, 141, 146, 154 compression, 33 concentrates, ix, 132 conduction, viii, 69 conductivity, 83, 89, 95, 96, 97, 99 conductors, viii, 70 configuration, 25, 58, 74 conjugation, 80, 89, 92, 95, 96, 97, 99 construction, 52, 132, 134 contradiction, 154 control, 139, 154 copper, 36, 38, 39, 41, 42, 43, 44, 71, 144 correlation, 118, 121, 125 coupling, 77, 78, 83 covalent bond, 45, 123 covalent bonding, 45 creatinine, 2, 16 crystal structure, vii, 1, 2, 5, 27, 30, 31, 32, 35, 36, 37, 40, 45, 51, 56, 57, 72, 74, 76, 77, 80, 84, 86, 89, 97, 109, 113, 121, 138, 154, 156 crystalline, vii, 5, 69, 79, 137, 154 crystallization, 9, 12, 32, 35, 90, 128 crystals, vii, 9, 34, 44, 71, 72, 73, 118, 123, 128, 137, 155, 159 D data collection, 110, 112 database, 106 definition, 105 degenerate, 78 dehydrate, 112, 114 density, 22, 27, 36, 110, 112 deposition, 98 derivatives, vii, viii, 2, 5, 7, 18, 49, 69 destruction, 139 deviation, 7, 8, 13, 16, 30, 31, 44, 48, 51, 56, 82 diffraction, 137, 138, 139, 144, 148 diffusion, ix, 153, 155 dimensionality, 134, 139, 148 dimerization, 49 dimethylformamide, 146, 154 disorder, 13, 22, 74, 77, 88, 92 disposition, 128 distortions, 39, 72 diversity, 121 DMF, 45, 46, 82, 98, 146, 154, 155, 156, 157 DNA, donors, 20, 38, 41 double bonds, drawing, 16, 133, 141 E earth, 44 electric field, 104 electrical conductivity, viii, 70, 78, 94 electrochemistry, 86 electrodes, 96 electron, 4, 11, 19, 20, 27, 36, 52, 71, 86 Index electronic structure, 64 electrons, 54, 70, 125 elongation, 33, 39, 44, 92 emission, 138 encapsulation, 135, 136 energy, 147 engineering, 118, 148, 153, 154 environment, 8, 13, 16, 24, 30, 49, 59, 147, 155 equilibrium, 125 ester, vii, ethanol, 41, 92, 106, 107, 135 europium, 58 F family, 56, 77, 106 films, 96, 97, 98 flexibility, 42, 128, 132 formula, vii, 1, 2, 13, 14, 36, 58, 89, 110, 112 fragments, 2, 52, 57, 110 frustration, 78 full capacity, 124 G generation, 90, 111, 148 geometrical parameters, 17 glutamate, 104 gold, 89 graphite, 107 H harvesting, 96 H-bonding, 17, 41, 111, 114, 121, 128 helicity, 118 homopolymers, 97 host, 56, 133, 134, 135, 147 hybrid, 97, 99, 142 hydrogen atoms, 9, 36, 107, 108 163 hydrogen bonds, 5, 12, 13, 14, 15, 18, 22, 35, 36, 37, 38, 53, 57, 109, 113, 122, 125, 128, 142, 146 hydroxyl, 14, 15, 19, 154 hydroxyl groups, 154 I identification, 35, 115 immersion, 140 in transition, inclusion, ix, 131, 132, 134, 136, 139 indication, 97 indices, 110, 112 industry, 104 infinite, 52, 54, 122, 134, 139, 141, 142 integrity, 136 interaction, 3, 9, 18, 28, 50, 82, 85, 94, 128 interactions, viii, 3, 9, 12, 16, 20, 22, 26, 28, 31, 38, 41, 50, 53, 58, 70, 74, 76, 77, 81, 82, 83, 86, 97, 103, 111, 136, 137, 144, 147, 148 intermolecular interactions, viii, 2, 70, 89, 94, 105, 111 inversion, 17, 28, 32, 35, 84, 88, 92, 111 iodine, 86 ionization, 134 ions, vii, ix, 2, 5, 9, 14, 16, 18, 20, 32, 35, 37, 39, 44, 49, 54, 56, 58, 108, 110, 111, 118, 121, 124, 132, 137, 139, 145, 147, 148, 153, 154, 155, 156, 157 IR spectra, 137, 140, 147 IR spectroscopy, 139 isolation, 71, 83, 90 isomers, 90, 105 K K+, 26, 54, 145 L labeling, 24, 35 164 Index lanthanide, 138 lasers, 104 limitation, 99 linearity, 34, 51 linkage, 96 links, 37, 50 lithium, 78 localization, 2, 17, 27, 54 low temperatures, 78 luminescence, 58 M magnesium, magnetic field, 77 magnetic moment, vii, 69 magnetic properties, viii, 70, 78, 83 magnetization, 77 majority, ix, 19, 72, 132 matrix, 107, 108, 159 measurement, 125 melting, 71 metal salts, 71, 83, 86, 134, 139, 148 metals, 5, 35, 84 methanol, 38, 39, 79 methyl groups, 22, 154, 156, 157 Mg2+, 147 microcrystalline, 90 microscopy, 148 mixing, 89 mobility, 144 model, 77 models, vii molecular structure, 35, 42, 51 molybdenum, 45 monomers, 49, 97 motif, 50, 124, 154 N Na+, 14, 25, 55, 57 NCS, 129, 130 Nd, 55 network, 9, 12, 28, 35, 41, 52, 53, 55, 57, 110, 121, 123, 140, 141, 154 nickel, 36, 38, 71, 79, 83, 88, 92, 96, 97, 99, 142 nicotinic acid, 106, 115 NIR, 94, 96, 97, 98 nitrogen, 2, 6, 8, 9, 10, 11, 13, 14, 16, 20, 22, 24, 25, 30, 35, 44, 47, 48, 51, 52, 54, 57, 115, 121 NMR, 49, 134 nodes, 148 nonlinear optics, nucleus, 42 O octane, 154 oligomers, 97 one dimension, 77 optical properties, vii, 69, 118, 128 order, 42, 96, 128, 136, 139, 155 organ, 72, 74 orientation, 19, 36, 74, 106, 115, 128 overlap, viii, 22, 70, 94 oxalate, 116, 117, 121, 124, 144 oxidation, vii, 2, 8, 25, 69, 71, 78, 79, 86, 87, 91, 92, 96, 98 oxygen, 2, 5, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 20, 22, 24, 25, 26, 27, 30, 32, 33, 34, 35, 36, 37, 38, 39, 44, 45, 48, 51, 54, 57, 58, 115 P pairing, 2, 51 palladium, 48, 49 parallel, 9, 12, 18, 32, 85, 124 parameter, 128 parameters, 16, 19, 73, 107, 108, 110, 112 PCP, 104 perchlorate, 117, 137, 142, 144, 145 performance, 95 permission, 3, 6, 7, 10, 11, 14, 15, 16, 17, 19, 20, 23, 26, 28, 29, 30, 31, 32, 33, 34, Index 36, 37, 38, 40, 41, 43, 44, 45, 46, 47, 48, 50, 51, 53, 54, 55, 56, 57, 58, 59 peroxide, perylene, viii, 69 pH, 34 phenol, 25, 32 phosphorus, 48 photoluminescence, ix, 132 photovoltaic devices, 96 physical properties, vii, 4, 104 platinum, 49, 96 polarizability, viii, 104, 115 polarization, 104 polymer, ix, 38, 39, 53, 95, 96, 97, 99, 137, 139, 147, 153, 155, 157 polymer films, 96 polymer structure, 95 polymeric chains, 15, 57 polymerization, 96, 97, 98 polymers, viii, ix, 43, 53, 54, 70, 94, 95, 96, 97, 99, 136, 138, 139, 148, 153, 154, 155, 156, 157 potassium, 10, 20, 25, 26 power, 78 preference, 104 pressure, 107 probability, 28, 29, 39, 74, 79, 84, 88, 93, 109, 113 probe, 83, 94 production, 90 program, 107, 108 propane, 136 properties, viii, 54, 70, 78, 89, 94, 95, 96, 97, 99, 104, 115, 128, 132, 134, 139, 142, 154 protons, 111, 123 purification, 87 purity, 91 pyrimidine, 113, 146 R radiation, 107 165 range, vii, viii, 7, 18, 25, 26, 30, 35, 37, 39, 40, 49, 52, 54, 56, 69, 70, 72, 86, 88, 110, 112 reactants, 34 reactions, 48, 134, 136, 139, 140, 141 recognition, ix, 131, 132, 134, 155 recommendations, iv recrystallization, 91 rings, viii, 10, 27, 39, 50, 72, 76, 80, 84, 88, 92, 94, 97, 103, 105, 106, 108, 112, 115, 121, 122, 124 room temperature, 78, 83, 86, 94, 107, 142 rubber, 104 rubidium, 27 ruthenium, 47 S salt, 18, 26, 31, 34, 54, 71, 72, 74, 78, 79, 80, 83, 84, 86, 88, 89, 90, 134, 135 salts, viii, 5, 25, 43, 54, 58, 71, 72, 73, 74, 76, 77, 79, 80, 83, 90, 96, 103, 105, 115, 136, 139, 140, 141, 143 scattering, 107 search, 49, 121, 155 selectivity, 136 self-assembly, 43, 45, 134 semiconductor, 83 sensing, 134 separation, 50, 58, 76, 142 shape, 115, 118, 136, 147 shares, 34 sharing, 16, 32 silver, 36, 135, 140, 141 single crystals, 72, 106, 107, 137 skeleton, 17 sodium, 5, 14, 16, 18, 30, 31, 35, 56, 144 software, 99 solid state, viii, 4, 51, 83, 89, 94, 103, 104, 105, 142, 148 solubility, 97 solvation, 105 solvent molecules, 143, 155, 156, 157 solvents, 97, 144, 154, 155 sorption, 146 166 Index sorption experiments, 146 space, viii, 10, 32, 49, 58, 103, 104, 108, 111, 117, 118, 137, 159 species, 31, 34, 70, 71, 78, 87, 90, 91, 92, 98, 108, 134, 135, 136, 138, 154 spectroscopy, 49, 96, 134 spectrum, 97 stabilization, 53 standard deviation, stoichiometry, 9, 16 storage, 142, 146 strain, 40, 49, 54 strategy, 128 strength, 121, 125 strontium, substitution, 19, 52 substitutions, 78 sulfur, viii, 70, 76, 78, 81, 85, 86, 89, 92 superconductivity, vii, 69 susceptibility, 86 symmetry, 7, 13, 15, 18, 19, 20, 22, 39, 49, 52, 56, 58, 104, 122, 125 synthesis, ix, 5, 35, 45, 57, 71, 72, 78, 83, 91, 96, 131, 134, 154 T temperature, 77, 86 tetrabutylammonium bromide, 79 tin, 52, 53 titanium, 6, topology, viii, 50, 131, 147 torsion, 48, 51, 105, 108, 113, 119, 121 trade, 104 transformation, 13, 140 transformations, 148 transition, viii, 4, 5, 7, 54, 70, 77, 136, 138 transition metal, 4, 5, 7, 54, 136, 138 transition metal ions, transition temperature, viii, 70 transmission, 107, 108 transportation, 139 trifluoroacetate, 117, 121 twinning, 72, 73 twist, 72, 80, 81 U uranium, 59 UV, 96, 97, 98 V valence, 96, 98 vanadium, 8, 10, 11, 12, 13, 14, 16, 18, 19, 21, 22, 24, 25, 26 W weak interaction, 17, 86 web, 130 workers, 132, 136, 144 X X-ray diffraction, viii, 45, 52, 104 Z zinc, ix, 134, 139, 153, 155, 157 ... https://www.novapublishers.com/catalog/index.php?cPath=23_29&seriespe= Chemistry+ Research+ and+ Applications CHEMISTRY RESEARCH AND APPLICATIONS CHEMICAL CRYSTALLOGRAPHY BRYAN L CONNELLY EDITOR Nova Science Publishers,.. .CHEMISTRY RESEARCH AND APPLICATIONS CHEMICAL CRYSTALLOGRAPHY No part of this digital document may be reproduced, stored... document is sold with the clear understanding that the publisher is not engaged in rendering legal, 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