DESIGN AND CONSTRUCTION OF COORDINATION POLYMERS · 2 Indium(III)–Organic Coordination Polymers with Versatile Topological Structures Based on Multicarboxylate Ligands 25 Lian Chen,

DESIGN AND CONSTRUCTIONOF COORDINATION POLYMERS

Edited by

MAO-CHUN HONG

LING CHEN

InnodataFile Attachment9780470467329.jpg


Edited by

MAO-CHUN HONG

LING CHEN

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Library of Congress Cataloging-in-Publication Data:

Design and construction of coordination polymers/

[edited by] Mao-Chun Hong and Ling Chen

Includes bibliographic references and index

ISBN 978-0-470-29450-5 (cloth)

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

http://www.copyright.comhttp://www.wiley.com/go/permissionhttp://www.wiley.com

Dedicated to

the Fujian Institute of Research on the Structure of Matter,

Chinese Academy of Sciences, on the occasion of

the fiftieth anniversary of its founding

and

Professor Xin-Tao Wu, one of the pioneers in the

development of the Fujian Institute, on the

occasion of his seventieth birthday

CONTENTS

Contributors xi

Preface xv

1 Coordinative Flexibility of Monovalent Silver in[AgI !L1]L2 Complexes 1Gerd Meyer, Muhamet Sehabi, and Ingo Pantenburg

1.1 Introduction, 1

1.2 Ligands L1 with 1,2 N-Donor Functions, 2



1.5 Conclusions, 19

References, 22

2 Indium(III)–Organic Coordination Polymers with VersatileTopological Structures Based on Multicarboxylate Ligands 25

Lian Chen, Fei-Long Jiang, Zheng-Zhong Lin, and Mao-Chun Hong

2.1 Introduction, 25

2.2 Architectures Constructed by In(III) and Benzenedicarboxylates, 27

2.3 Architectures Constructed by In(III) and Benzenetricarboxylates, 35

2.4 Architectures Constructed by In(III) and Other

Benzenemulticarboxylates, 49

2.5 Luminescence, Ion Exchange, and Hydrogen Storage, 55

2.6 Conclusions, 56

References, 59

vii

3 Crystal Engineering of Coordination Polymers viaSolvothermal In Situ Metal–Ligand Reactions 63

Jie-Peng Zhang and Xiao-Ming Chen


3.2 Metal-Redox Reaction, 65

3.3 Conversion of Carboxylic Acid, 69

3.4 Carbon–Carbon Bond Formation, 72

3.5 Heterocycle Formation from Small Molecules, 75

3.6 Transformation of Sulfur-Containing Ligands, 81

3.7 Conclusions, 83

References, 84

4 Construction of Some Organic–Inorganic HybridComplexes Based on Polyoxometalates 87

Can-Zhong Lu, Quan-Guo Zhai, Xiao-Yuan Wu, Li-Juan Chen,

Shu-Mei Chen, Zhen-Guo Zhao, and Xiao-Yu Jiang


4.2 Complexes Built Up by POMs with 1,2,4-Triazolate

and Its Derivatives, 88

4.3 Complexes Built Up by Molybdenum Oxide Chains

with Pyridine Derivatives, 102

4.4 Conclusions, 107

References, 108

5 Silver(I) Coordination Polymers 111

Cheng-Yong Su, Chun-Long Chen, Jian-Yong Zhang, and Bei-Sheng Kang


5.2 Coordination Geometries of Agþ Ions, 1125.3 Ligands in Silver(I) Coordination Polymers, 121

5.4 Supramolecular Interactions and Counter Anions

in Silver(I) Coordination Polymers, 128

5.5 One- to Three-Dimensional Coordination Polymers

Based on Silver–Ligand Coordination Bonds, 130

5.6 Intertwining or Interpenetrating of Silver(I)

Coordination Polymers, 135

5.7 Properties of Silver(I) Coordination Polymers, 137References, 139

6 Tuning Structures and Properties of Coordination Polymersby the Noncoordinating Backbone of Bridging Ligands 145

Miao Du and Xian-He Bu


6.2 Ligand Design for Coordination Polymers, 146

viii CONTENTS

6.3 Role of Noncoordinating Backbones of Bridging Ligands, 150


References, 165

7 Ferroelectric Metal–Organic Coordination Compounds 71

Heng-Yun Ye, Wen Zhang, and Ren-Gen Xiong


7.2 Homochiral Discrete or Zero-Dimensional MOCCs, 173

7.3 Acentric MOCPs Produced by Supramolecular

Crystal Engineering, 179

7.4 Homochiral MOCPs Constructed with Optical

Organic Ligands, 183


References, 192

8 Constructing Magnetic Molecular Solids by EmployingThree-Atom Ligands as Bridges 195

Xin-Yi Wang, Zhe-Ming Wang, and Song Gao


8.2 Coordination Characteristics of Three-Atom Bridges

and Their Role in Mediating Magnetic Interaction, 197

8.3 Co-Ligands, Templating Cations, and Other Short Bridges, 200

8.4 Magnetic Molecular Solids Based on Three-Atom Bridges, 202


References, 223

9 Structures and Properties of Heavy Main-Group Iodometalates 229

Li-Ming Wu and Ling Chen


9.2 Structural Features of Iodobismuthates and Iodoplumbates, 230

9.3 Structural Modification, 249

9.4 Optical and Thermal Properties, 255

9.5 Summary, 262

References, 263

10 Cluster-Based Supramolecular Compounds fromMo(W)/Cu/S Cluster Precursors 267

Jian-Ping Lang, Wen-Hua Zhang, Hong-Xi Li, and Zhi-Gang Ren


10.2 Strategies for Design and Assembly, 268

10.3 Structural Features, 273

10.4 Luminescent and Third-Order Nonlinear Optical Properties, 298

CONTENTS ix


References, 302

11 Microporous Metal–Organic Frameworks as FunctionalMaterials for Gas Storage and Separation 307

Long Pan, Kun-Hao Li, JeongYong Lee, David H. Olson, and Jing Li


11.2 Design, Rational Synthesis, and Structure Description, 309

11.3 Structure Stability, Permanent Microporosity, and

Hydrogen Adsorption, 322

11.4 Hydrocarbon Adsorption, 332

11.5 Ship-in-Bottle Synthesis, 348

11.6 Summary and Conclusions, 349

References, 350

12 Design and Construction of Metal–Organic Frameworksfor Hydrogen Storage and Selective Gas Adsorption 353

Sheng-Qian Ma, Christopher D. Collier, and Hong-Cai Zhou


12.2 Hydrogen Storage in Porous Metal–Organic Frameworks, 354

12.3 Porous Metal–Organic Frameworks for Selective

Gas Adsorption, 366

12.4 Outlook, 369

References, 370

13 Structure and Activity of Some BioinorganicCoordination Complexes 375

Jin-Tao Wang, Yu-Jia Wang, Ping Hu, and Zong-Wan Mao


13.2 Biomimetic Modeling of a Metalloenzyme with a

Cluster Structure, 376

13.3 Bioinspired Complexes with a Recognition Domain, 384

13.4 Functional Complexes as Therapeutic Agents, 391


References, 401

Index 405

x CONTENTS

CONTRIBUTORS

Xian-He Bu, Department of Chemistry, Nankai University, Tianjin, People’s

Republic of China

Chun-Long Chen, MOE Laboratory of Bioinorganic and Synthetic Chemistry,

State Key Laboratory of Optoelectronic Materials and Technologies, School

of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou,

People’s Republic of China

Lian Chen, State Key Laboratory of Structural Chemistry, Fujian Institute of

Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou,

Fujian, People’s Republic of China

Ling Chen, State Key Laboratory of Structural Chemistry, Fujian Institute of



Li-Juan Chen, State Key Laboratory of Structural Chemistry, Fujian Institute of



Shu-Mei Chen, State Key Laboratory of Structural Chemistry, Fujian Institute of



Xiao-Ming Chen, MOE Laboratory of Bioinorganic and Synthetic Chemistry,

School of Chemistry and Chemical Engineering, Sun Yat-Sen University,

Guangzhou, People’s Republic of China

xi

Christopher D. Collier, Department of Chemistry and Biochemistry, Miami

University, Oxford, Ohio

Miao Du, College of Chemistry and Life Science, Tianjin Normal University,

Tianjin, People’s Republic of China

Song Gao, State Key Laboratory of Rare Earth Materials and Applications,

College of Chemistry and Molecular Engineering, Peking University, Beijing,


Mao-Chun Hong, State Key Laboratory of Structural Chemistry, Fujian Institute

of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou,


Ping Hu, MOE Laboratory of Bioinorganic and Synthetic Chemistry, School of

Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou,


Fei-Long Jiang, State Key Laboratory of Structural Chemistry, Fujian Institute of



Xiao-Yu Jiang, State Key Laboratory of Structural Chemistry, Fujian Institute ofResearch on the Structure of Matter, Chinese Academy of Sciences, Fuzhou,


Bei-Sheng Kang, MOE Laboratory of Bioinorganic and Synthetic Chemistry,




Jian-Ping Lang, College of Chemistry, Chemical Engineering andMaterials Science,

Suzhou University, Suzhou, Jiangsu, People’s Republic of China

JeongYong Lee, Department of Chemistry and Chemical Biology, Rutgers Univer-

sity, Piscataway, New Jersey

Hong-Xi Li, College of Chemistry, Chemical Engineering and Materials Science,


Jing Li, Department of Chemistry and Chemical Biology, Rutgers University,Piscataway, New Jersey

Kun-Hao Li, Department of Chemistry and Chemical Biology, Rutgers University,

Piscataway, New Jersey

Zheng-Zhong Lin, State Key Laboratory of Structural Chemistry, Fujian Institute

of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou,


xii CONTRIBUTORS

Can-Zhong Lu, State Key Laboratory of Structural Chemistry, Fujian Institute of



Sheng-Qian Ma, Department of Chemistry and Biochemistry, Miami University,

Oxford, Ohio

Zong-Wan Mao, MOE Laboratory of Bioinorganic and Synthetic Chemistry,



Gerd Meyer, Institut f€ur Anorganische Chemie, Universit€at zu K€oln, K€oln,Germany

David H. Olson, Department of Chemistry and Chemical Biology, Rutgers

University, Piscataway, New Jersey

Long Pan, Department of Chemistry and Chemical Biology, Rutgers University,

Piscataway, New Jersey

Ingo Pantenburg, Institut f€ur Anorganische Chemie, Universit€at zu K€oln, K€oln,Germany

Zhi-Gang Ren, College of Chemistry, Chemical Engineering andMaterials Science,


Muhamet Sehabi, Institut f€ur Anorganische Chemie, Universit€at zu K€oln, K€oln,Germany

Cheng-Yong Su, MOE Laboratory of Bioinorganic and Synthetic Chemistry,State Key Laboratory of Optoelectronic Materials and Technologies, School



Jin-Tao Wang, MOE Laboratory of Bioinorganic and Synthetic Chemistry, Schoolof Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou,


Xin-Yi Wang, State Key Laboratory of Rare Earth Materials and Applications,



Yu-Jia Wang, MOE Laboratory of Bioinorganic and Synthetic Chemistry, School



Zhe-Ming Wang, State Key Laboratory of Rare Earth Materials and Applications,



CONTRIBUTORS xiii

Li-Ming Wu, State Key Laboratory of Structural Chemistry, Fujian Institute of



Xiao-Yuan Wu, State Key Laboratory of Structural Chemistry, Fujian Institute of



Ren-Gen Xiong, Ordered Matter Science Research Center, Southeast University,

Nanjing, People’s Republic of China

Heng-Yun Ye, Ordered Matter Science Research Center, Southeast University,


Quan-Guo Zhai, State Key Laboratory of Structural Chemistry, Fujian Institute of



Jian-Yong Zhang, MOE Laboratory of Bioinorganic and Synthetic Chemistry,




Jie-Peng Zhang, MOE Laboratory of Bioinorganic and Synthetic Chemistry,



Wen Zhang, Ordered Matter Science Research Center, Southeast University,


Wen-Hua Zhang, College of Chemistry, Chemical Engineering and MaterialsScience, Suzhou University, Suzhou, Jiangsu, People’s Republic of China

Zhen-Guo Zhao, State Key Laboratory of Structural Chemistry, Fujian Institute of



Hong-Cai Zhou, Department of Chemistry and Biochemistry, Miami University,

Oxford, Ohio; now at the Department of Chemistry, Texas A&M University,

College Station, Texas

xiv CONTRIBUTORS

PREFACE

This volume, Design and Construction of Coordination Polymers, is published in

recognition of the fiftieth anniversary of the beginning of the Fujian Institute of

Research on the Structure ofMatter, Chinese Academy of Science, and is dedicated to

Prof. Xin-TaoWu, on the occasion of his seventieth birthday. The volume contains 13

chapters that focus on this theme, contributed by former graduates and friends of this

institution. They span awide range of topics, systems, and approaches to coordination

polymers. In Chapter 1, G. Meyer and co-workers describe a variety of AgL1L2coordination complexes achieved with mixed N-containing ligands, some of which

exhibit particularly short Ag--N distances. A series of indium(III)–carboxylatecoordination polymers with a variety of dimensionalities are reported in Chapter 2

by M.-C. Hong and colleagues. Following this, in Chapter 3, X.-M. Chen and co-

workers examine an interesting series of coordination polymers that are formed by

solvothermal reactions between diverse metals and ligands, covering a variety of

functionalities and reaction types. In Chapter 4, C.-Z. Lu and co-workers report on a

variety of hybrid polyoxometallates built of oxo-Mo, oxo-Cu, and oxo-Ag centers and

1,2,4-triazolate or pyridine derivatives. In Chapter 5, C.-Y. Su and others describe the

range of Ag(I) coordination environments that can be obtained with various ligand

types as well as interpenetrating polymers and their diverse properties and applica-

tions. A different type of variety results when coordination polymers are tuned via

systematic variations in the bridging organic backbones within multidentate ligands,

as related by X.-H. Bu and others in Chapter 6.

Chapter 7, by R.-G. Xiong and co-workers, features a different direction, the

design and synthesis of ferroelectric coordination compounds or polymers that are

constructed of monochiral ligands and occur in polar space groups. The generation

and properties of paramagnetic solids of different dimensionalities from three-atom

xv

bridging ligands and 3d metal ions are described by S. Gao and colleagues in

Chapter 8. In Chapter 9, L.-M. Wu and L. Chen describe and explain structural,

optical, and thermal properties of various iodometallic phases of Pb or Bi with

different dimensionalities and motifs. J.-P. Lang and co-workers relate in Chapter 10

the design, construction, and optical properties of supramolecular cluster-based

phases of Mo(W)/Cu/S. Microporous metal–organic frameworks as materials for

gas storage and separation are addressed in Chapter 11 by J. Li and colleagues. In

Chapter 12, H.-C. Zhou and co-workers enumerate the design, construction, and

properties of various metal–organic frameworks for storage and separation of gases,

H2 in particular. Finally, in Chapter 13, Z.-W. Mao and colleagues outline the

application of some bioinorganic coordination compounds as mimics or models for

a range of biological functions or therapeutic agents. Enjoy!

We are grateful for all the authors who unselfishly spent their most precious time in

writing contributions for the volume and meeting deadlines. Special thanks are given

to Prof. Thomas C.W.Mak at the Chinese University of Hong Kong, Prof. Bei-Sheng

Kang at Sun Yat-Sen University, Guangzhou and Prof. Qiu -Tian Liu at FIRSM for

their kind help, andA. Lekhwani andR.Amos of JohnWiley&Sons, Inc. for editorial

assistance.

MAO-CHUN HONG

LING CHEN

Fuzhou

August 2008

xvi PREFACE

1COORDINATIVE FLEXIBILITYOF MONOVALENT SILVER IN[AgI L1]L2 COMPLEXESGERD MEYER, MUHAMET SEHABI, AND INGO PANTENBURG

Institut f€ur Anorganische Chemie, Universit€at zu K€oln, K€oln, Germany

1.1 INTRODUCTION

Monovalent silver, Agþ , is a fifth-period closed-shell d10-ion. It is therefore oftenconsidered a pseudo-alkali-metal cation with an ionic radius close to that of Naþ , 114versus 113 pm for coordination number (CN) 4 [1]. Indeed, AgCl crystallizes with

an NaCl type of structure, with a¼ 554.9 versus a¼ 563.9 pm [2]. On the other hand,many physical properties are quite different. One striking example is that of AgCl

and NaCl solubilities in water, 1.88� 10�3 g /L versus 358 g/L [3]. The solubility ofAgCl is enhanced dramatically through the addition of aqueous ammonia, and

linear [Ag(NH3)2]þ cations are formed. Quite obviously, there is a much larger

affinity of Agþ toward the N-donor ligand ammonia than toward water or chloride ascompeting ligands.

There are many complex salts of the [Ag(NH3)2]þ cation with common

inorganic cations, NO3� or ClO4

� (see, e.g., ref. 4). In [Ag(NH3)2](ClO4),the [H3N--Ag--NH3]

þ complex cation is linear by symmetry in both the high- andlow-temperature modifications [4d]. The Ag--N distances are 214 pm, on average, at170K. The cations are arranged such that the shortest Ag--Ag contacts are 302 pm,well above the Ag--Ag distance of 288.9 pm inmetallic silver but below the sum of the

Design and Construction of Coordination Polymers, Edited by Mao-Chun Hong and Ling ChenCopyright � 2009 John Wiley & Sons, Inc.

1

van der Waals radii of 344 pm. However, argentophilicity [5] (i.e., d10–d10 bonding

interactions at a level of weak hydrogen bonds) may be associated with these short

distances. Argentophilicity appears to be a slightly smaller effect than aurophilicity,

judging by the Agþ --Agþ and Auþ --Auþ distances in the isostructural compounds[Ag(NH3)2](ClO4) [4d] and [Au(NH3)2](ClO4) [6] at the same temperature (170K):302.0(2) and 299.0(1) pm, respectively. Much shorter Ag--Ag distances maybe seen in constrained systems, of which the dimeric structure of the simple silver

acetate is perhaps the most spectacular example, with d(Ag--Ag)¼ 279.4(4) to280.9(3) pm [7].

Hg2þ as a diagonally related d10-ion forms analogous linear complexes,[Hg(NH3)2]

2þ , with Hg--N distances of 207.2(16) pm in [Hg(NH3)2][HgCl3]2 [8],shorter than d(Ag--N)¼ 212.9(11) to 216.0(12) pm in [Ag(NH3)2](ClO4) [4d]but larger than d(Au--N)¼ 205.2(2) in [Au(NH3)2](ClO4) [6]. Mercuriphilic effectshave not been observed, perhaps due to the higher charge. On the other hand,

relativistic effects are, for HgII as for AuI, much more pronounced than for AgI.

One evidence of these effects in mercuric chemistry is the pronounced preference

for linear two-coordinate complexes [9], also termed as characteristic coordination

number (CCN) 2 [10].

As relativistic effects are much less important in silver chemistry, AgI exhibits a

much larger coordinative flexibility, apparent in coordination numbers between 2 and

6 and in typical closed-shell ion coordination polyhedra (as closed as possible). Other

than the hard (Pearson acid) alkali-metal ions, the Agþ ion is muchmore polarizable:thus is a much softer Pearson acid with a higher tendency to coordinate to softer

Pearson bases, hence with higher covalent bonding contributions.

In this chapter we report on a number of recently discovered AgI complexes with

multi-N donor ligands [11] but do not consider this work a comprehensive review. The

fact that silver coordination chemistry [12] is presently a rather hot topic may also be

seen from a series of leading-edge research papers which have recently been

published in the Australian Journal of Chemistry [13]. Silver complexes may have

a number of functionalities; they may conduct electric current or luminesce, or they

may have antimicrobial activity [14], to name only two.

As ammonia (NH3) is the parent of all N-donor ligands, Ag--Ndistances as short as,say, 210 pm are considered the landmark for the strongest Agþ N interactions(“bonds”) possible in [AgI L1]L2 coordination compounds. L1 is usually a neutralN-donor ligand and L2 is an auxiliary ligand (co-ligand) with a negative charge

competing with the L1 ligand for space in the coordination sphere of Agþ .

1.2 LIGANDS L1 WITH 1,2 N-DONOR FUNCTIONS

1,2-Pyrazole has two directly neighboring nitrogen functions. As competing

L2 ligands, triangular (NO3�), tetrahedral (BF4

�, ClO4�, SO4

2�), and octahedralanions (PF6

�) as well as trifluoroacetate (CF3COO�¼Tfa�) were attempted. In all

of these, pyrazole coordinates as a neutral ligand with N2, which bears no

hydrogen atom.

2 COORDINATIVE FLEXIBILITY OF MONOVALENT SILVER

In [Ag(Pyz)2](BF4) (1), the isotypic [Ag(Pyz)2](ClO4) (2), and in Ag(Pyz)(NO3)(3), we observe truly linear N--Ag--N environments (Fig. 1.1), whereas in[Ag(Pyz)2]2(PF6)2(Pyz) (4) theN--Ag--Nangle is bent by a fewdegrees (seeTable 1.1).Cations and anions seem to be independent of each other in 1, 2, and 4, which all have

1 : 2 : 1 (Ag : L1 : L2) stoichiometries. In the nitrate (3), with its unusual 1 : 1 : 1

FIGURE 1.1 Linear, triangular, and tetrahedral environments of Agþ in [Ag(Pyz)2](BF4)(1), [Ag(Pyz)3](Tfa) (5), and [Ag(Pyz)4]2(SO4) (6).

LIGANDS L1 WITH 1,2 N-DONOR FUNCTIONS 3

TABLE1.1

CoordinationNumbersandGeometry,Distances,andAnglesoftheAgI –N

DonorComplexes

Compound

CN

CoordinationGeometry

d(A

g–N)/pm,

d(Ag–O)/pm

<(N

–Ag–N)/�

CCDCNo.

[Ag(Pyz)

2](BF4)(1)

2Linear,isolated

212.0(3),213.1(3)

180

662474

[Ag(Pyz)

2](ClO

4)(2)

2Linear,isolated

214.4(7),216.4(7)

180

662475

Ag(Pyz)(N

O3)(3)

2Linear,isolated

212.6(3),240.3(4)

180

662476

[Ag(Pyz)

2](PF6)(Pyz)

(4)

2Linear,isolated

211.7(5)–212.8(5)

174.7(2),177.3(2)

662477

[Ag(Pyz)

3](Tfa)(5)

3Trigonal,isolated

220.1(3)–227.5(3)

107.4(1)–142.7(1)

662478

[Ag(Pyz)

4] 2(SO4)(6)

4Tetrahedral,isolated

223.9(1)–239.9(1)

96.5(3)–125.5(3)

662479

Ag(D

cp)(OAc)

(7)

2 4

Linearþ

tetrahedral,

double

chain

218.4(3),249.2(4),

227.6(3)

170.1(2),95.0(1)

662480

Ag(D

cp)(Tfa)(8)

2 4

Linearþ

tetrahedral,

double

chain

218.2(4),244.1(4),

228.9(4)

172.2(2),93.8(2)

662481

Ag(D

cp) 2(BF4)(9)

4Tetrahedral,chain

233.3(3),250.7(3)

85.2(2)–137.6(1)

662482

Ag(D

cp) 2(ClO

4)(10)

4Tetrahedral,chain

233.4(2),251.2(2)

83.3(1)–137.6(1)

662483

[Ag(M

el) 2](BF4)(11)

2Linear,isolated

215.4(3),216.8(3)

170.7(1)

662484

[Ag(M

el) 2](BF4)(Mel) 2

(12)

2Linear,isolated

213.1(2),213.6(2)

176.5(1)

662485

Ag(M

el) 2(Tfa)(H2O)(13)

4þ

1Pyramidal,chain

229.7(6),232.8(6),

245.4(6)

172.2(2)

662486

Ag(M

el)(NO3)(14)

2þ

2Bent,chain

225.3(5),229.0(4),

257.6(6)

126.6(2)

662487

[Ag(D

pt)2(N

O3)]2(15)

2þ

2Bent,dim

er220.6(4),221.9(6),

282.6(4)

145.4(2)

662488

4

[Ag(D

pt)2(O

Ac)] 2

(16)

2þ

2Tetrahedral,dim

er230.1(4),235.3(5),

237.4(3)

122.8(2)

662489

Ag(D

pt)(H

2O)(ClO

4)(17)

2þ

1Bent,chain

228.2(5),240.2(5),

240.1(7)

111.2(2)

662490

Ag(Bpy) 2(ClO

4)(18)

4Square,

monomer

227.6(3)–243.0(3)

71.4(1)–159.2(1)

662491

Ag(Bpy)(Tfa)(19)

2þ

1Trigonal,weakdim

er229.7(4),232.2(4),

218.2(3)

72.0(1)

662492

Ag(Bpq) 2(Tfa)(20)

4þ

2Trigonal

prism

,

monomer

240.5(12)–248.7(13),

233.9(10)–267.8(13)

68.2(4)–153.0(4)

662493

Ag2(Bpq)(NO3) 2

(21)

1þ

3

2þ

2

Chain

227.9(3),238.2(2)–

252.2(2)

70.3(1)

662494

236.4(3),243.5(2),

240.5(2),242.0(2)

Ag(Tpt)(N

O3)(22)

3þ

1Windingchain

242.7(4)–261.3(4),

236.1(4)

63.9(1)–136.0(2)

662495

Ag4(Tpt)2(Tfa) 4(H

2O)(23)

3þ

2Tetramers,stairs

238.6(7)–253.1(9),

225.6(7),276.0(2)

65.9(3)–133.8(2)

662496

2þ

2222.3(7),264.7(5),

220.9(6),274.0(3)

[Ag(Pip)](BF4)(24)

2Linear,isolated

216.6(7),217.4(9)

174.1(2)

662497

[Ag2(Pip) 3](Tfa) 2(H

2O) 6

(25)

3Trigonal,layer

226.3(2),229.1(2),

239.2(2)

104.6(1),116.9(1),137.6(1)

662498

[Ag(Pip) 2](NO3)(26)

4Tetrahedral,waved

layer

238.6(4),239.4(4),

245.2(4),245.6(5)

89.9(2)–116.6(2)

662499

5

stoichiometry, however, there are two symmetrically and functionally independent

Agþ ions. One is, as above in 1, 2, and 4, incorporated in the linear [Ag(Pyz)2]þ

cation. The second Agþ ion has four contacts to C3 and C4 of pyrazole withd(Ag--C)¼ 249.4(4) and 281.8(5) pm and to two oxygen atoms of two nitrate ions atd(Ag--O)¼ 240.3(4) pm, such that a chain of the stoichiometry Ag(Pyz)2Ag(NO3)2 iscreated (see Fig. 1.2). [Ag(Pyz)3](Tfa) (5) and [Ag(Pyz)4]2(SO4) (6) exhibit triangular

and tetrahedral environments, respectively, as the 1 : 3 and 1 : 4 stoichiometries of

FIGURE 1.2 (a) Part of a � � �Ag(Pyz)2Ag(NO3)2 � � � chain as observed in the crystalstructure of Ag(Pyz)(NO3) (3); (b) the surrounding of (SO4)

2� by four [Ag(Pyz)4]þ cations

stabilized by N–H � � �O hydrogen bonding in the crystal structure of [Ag(Pyz)4]2(SO4) (6).


Ag : L1 suggest (see Fig. 1.1). Distances increase steadily with coordination numbers

(see Table 1.1). Angles in the AgN3 triangles and AgN4 tetrahedra of 5 and 6 cover a

rather wide range (Table 1.1); hence, these coordination polyhedra are rather

distorted. The sulfate ion in 6 is surrounded by four [Ag(Pyz)4]þ cations and appears

to form hydrogen bonds to N--H hydrogen atoms with d(N--H � � �O) between 193 and207 pm (see Fig. 1.2).


Although pyrazole has two possible nitrogen functions, --N| and --N--H, the free pairof electrons of the --N| function binds only to Agþ with distances dependent on thecoordination number.

Pyrimidine (1,3-diazine, Pym) has two --N| functions in the 1,3 positions.Both functions are used to form coordination polymers in the pyrimidine derivative

2,4-diamino-6-chloropyrimidine (Dcp) when acetate (OAc�) or trifluoroacetate(Tfa�) are the competing L2 ligands [15]. As chelating anions, these are incorporatedas bridging ligands in the essentially isostructural compounds Ag(Dcp)(OAc) (7) and

Ag(Dcp)(Tfa) (8). There are two crystallographically and functionally independent

Agþ cations in the structures, both of which are coordinated by two --N| functions ofDcp. These --N| functions are different, as one (N3) is neighboring the C4--Cl functionand the other one is opposite it (N1). Ag1 is almost linearly coordinated by two

N3 atoms at d(Ag--N)¼ 218.4(4) pm and

cations with Ag--N distances of 215.4(3) pm and an N--Ag--N angle of 170.7(1)�. Thisangle might be due to a weak attraction to one fluorine atom of the (BF4)

� anion,d(Ag--F)¼ 284.4(3) pm (Fig. 1.4). An analogous almost linear cation [Ag(Mel)2]þwith even slightly smaller Ag--N distances [213.1(2), 213.6(2) pm] is seen in[Ag(Mel)2](BF4)(Mel)2 (12). Two solvent molecules of melamine are very loosely

attached to the [Ag(Mel)2]þ cationswith amino functions at distances of 287.3(3) and

302.0(3) pm (see Fig. 1.4).

FIGURE 1.3 (a) Part of the Ag2(Dcp)4/2(OAc)2 chain as observed in the crystal structure of

Ag(Dcp)(OAc) (7) and analogously in the crystal structure of Ag(Dcp)(Tfa) (8); (b) part

of the [Ag(Dcp)2]þ chain as observed in the crystal structures Ag(Dcp)2(BF4) (9) and

Ag(Dcp)2(ClO4) (10).


With the somewhat stronger ligands trifluoroacetate and nitrate, chain structures

are formed with melamine acting as a bridging m2 ligand. The coordination environ-ment around AgI in Ag(Mel)2(Tfa)(H2O) (13) is a (distorted) square pyramid with

four --N| functions of four melamine molecules forming the base at Ag--N distancesof 229.7(6) and 232.8(6) pm and an apical oxygen atom of one Tfa� anion atd(Ag--O)¼ 245.4(6) pm. The Ag(Mel)4(Tfa) units bridge via neighboring --N|functions to chains with the AgN4O pyramids directed alternately up and down

FIGURE 1.4 (a) [Ag(Mel)2]þ cations to which X¼ (BF4)�/(ClO4)� are loosely attached in

the crystal structure of [Ag(Mel)2]X (11); (b) the [Ag(Mel)2]+ cation to which two melamine

molecules are loosely attached in [Ag(Mel)2](BF4)(Mel)2 (12).

LIGANDS L1 WITH 1,3 N-DONOR FUNCTIONS 9

(Fig. 1.5). The nitrate ligand influences the coordination sphere around AgI much

more than does trifluoroacetate. This is documented more clearly by the much more

bent N--Ag--N part [126.6(2)�] than by the Ag--N distances (see Table 1.1 and ref. 20).The 1 : 1 : 1 stoichiometry also affords a chain structure with neighboring --N|functions of melamine ligand bridging (see Fig. 1.5).

A similar m2 bridging coordination mode was recently found in Cu2(Mel)Br2.In Cu3(Mel)Cl3 melamine even acts as a m3 bridging ligand using all three --N|functions [21]. Hydrogen bonding between the amino-H atoms and the halogen atoms

is made responsible for the formation of two- and three-dimensionally extended

structures.

In the ligand 2,4-diamino-6-phenyl-1,3,5-triazine (Dpt), one amino ligand of

melamine is substituted by a phenyl ring. With nitrate as L2 and the stoichiometry

FIGURE1.5 (a) Ag(Mel)4/2(Tfa) chains in the crystal structure ofAg(Mel)2(Tfa)(H2O) (13);

(b) part of the Ag(Mel)2/2(NO3) chains in the crystal structure of Ag(Mel)(NO3) (14).


1 : 2 : 1, a dinuclear complex [Ag(Dpt)2(NO3)]2 is formed in (15) with bent

[Ag(Dpt)2]þ cations [

Acetate also functions as a bridging ligand in the crystal structure of

Ag(Dpt)2(OAc) (16), such that, again, dimeric units are formed. While nitrate acts

as a monodentate ligand, acetate functions as a bidentate bridging ligand (Fig. 1.6).

Acetate acts as a much stronger ligand, which is demonstrated by the much

smaller N--Ag--N angle, shorter Ag--O distance, and longer Ag--N distance (seeTable 1.1).

The crystal structure of Ag(Dpt)(H2O)(ClO4) (17) is special in that Agþ has a

coordination number of 1 þ 1 þ 1 with bridging Dpt ligands forming a chain andone water molecule coordinating with the central Agþ ion. One Ag--N distance israther short [228.2(5) pm]; the other is equal to the Ag--OH2 distance [240.1(7)pm]. The chains run down the b-axis and are arranged such that layers appear

between which the ClO4� ions and the coordinating water molecules are included

(Fig. 1.7).


2,20-Bipyridine (Bpy) is one of simplest ligands, with a cisoid N--C--C--N function;hence it usually acts as a bidentate ligand. In Ag(Bpy)2(ClO4) (18) [22], Ag

þ hasan unusually squarelike environment with rather strong deviations of the N--Ag--Nangles from 90� (see Table 1.1), subject mainly to the bite distance, d(N--N)¼ 271.4(13) pm in the Bpy ligand and to the torsion angle between the two pyridyl rings of

12.6(5)�. The [Ag(Bpy)2]þ cations form a chain in the crystallographic [0 1 0]

direction with Ag--Ag distances of 366.6(1) pm and an Ag--Ag--Ag angle of152.4(1)�, where some p--p stacking interactions might be involved [23] (Fig. 1.8).The (ClO4)

� anions act as “noncoordinating” anions; they provide electroneutralityand are not really involved in coordinationwithAgI, the shortest Ag--Odistance being496.8(5) pm.

In Ag(Bpy)Tfa (19) [22], a very similar five-membered ring to that of

Ag(Bpy)2(ClO4) is observed, with Ag--N distances of 229.7(4) and 232.2(4) pm andan N--Ag--N angle of 72.0(1)�. However, in contrast to 18, 19 forms a molecular,triangular complex Ag(Bpy)Tfa. These complexes are stacked to dimers with

surprisingly short Ag--Agdistances of 303.73(9) pm (see Fig. 1.8). Hydrogen bondingbetween the fluorine atoms of the trifluormethyl substituents and phenyl-H atoms

appears to be further stabilizing, with d(F � � �H)¼ 294 and 299 pm.Judging from these two Ag--Bpy complexes, with a very weakly coordinating

(ClO4)� ligand and a considerably stronger Tfa� ligand competing with 2,20-

bipyridine, AgI appears to prefer rather small coordination numbers with rather

strong Ag--N bonding interactions. Recently, we have also been investigating MnII

complexes with bypyridine and a variety of other N-donor ligands [24]. In all of these,

MnII prefers an octahedral coordination environment: for example, in the simple

Mn(Bpy)2cis-Br2, withMn--N distances around 230 pm.With a 1 : 1 : 2 stoichiometryin Mn(Bpy)Br2, zigzag chains of edge-sharing MnN2Br4 octahedra are formed with

d(Mn--N)¼ 226.3(3) pm. However, despite the different coordination numbers, the


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DESIGN AND CONSTRUCTION OF COORDINATION POLYMERS · 2 Indium(III)–Organic Coordination Polymers with Versatile Topological Structures Based on Multicarboxylate Ligands 25 Lian Chen,