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Journal logoSTRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Coordination polymers (July 2014)

Introduced by Len Barbour

The past two decades have witnessed a veritable explosion of reports detailing the solid-state structures of coordination compounds consisting of conceptually infinite one-dimensional chains, two-dimensional nets and three-dimensional frameworks. The concepts involved are relatively simple; crystalline coordination polymers are most often formed from solutions containing metal ions and bridging ligands. The seemingly unlimited opportunities for preparing novel coordination polymers arise not only from obvious choices that influence structural topology (i.e. bridging ligand geometry and metal ion coordination mode) but also from a range of other factors, some of which can be quite subtle. The collection of articles selected for this virtual issue serves to showcase the amazing diversity of the field. The issue collects together a series of articles originally published in the journal between January 2012 and December 2013.

Highlighted illustration

Cover illustration: A layer of edge-shared Ca pentagonal-bipyramidal polyhedra forming six-membered rings, viewed along the c axis, with succinate ligands shown in ball-and-stick representation. See Mazaj et al. [Acta Cryst. (2012), C68, m4-m6].













































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The title structure con­tains two kinds of independent one-dimensional chain, viz. {[Cd(C8H15N2O2)Cl2]+}n and {[CdCl3(H2O)]}n, and uncoordinated water mol­ecules. Each CdII cation in the former chain is octa­hedrally coordinated by two pairs of bridging chloride ligands and two O atoms from different bridging carboxyl­ate groups, while CdII cations in the latter chain are octa­hedrally surrounded by four bridging chloride ligands, one terminal chloride ligand and one coordinated water mol­ecule.

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The structural unit consists of one C2-symmetric [NbOF4] anion, where the NbV centre is five-coordinated by four F atoms and one O atom in the first coordination shell, forming a square-pyramidal coordination geometry, and of one centrosymmetric coordinated [Cu2(obpy)2]+ cation (obpy is 2,2′-bipyridin-6-olate), in which the oxidation state of each Cu site is disordered, which is confirmed by XPS results.

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Single-crystal structural analysis reveals that the title complex is a one-dimensional polymeric chain, which is further extended to a three-dimensional supra­molecular network via a combination of hydrogen-bonding and aromatic stacking inter­actions.

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In CuI and AgI ladder-like coordination polymers, two metal ions are linked by two 2-ethyl-1-(pyridin-3-ylmeth­yl)-1H-benzimidazole ligands (bep) to form a centrosymmetric 18-membered M2(bep)2 metallacycle, while adjacent M2(bep)2 metallacycles are further inter­linked by another two bep ligands resulting in a ladder-like array.

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The structure of a nickel compound with a three-dimensional polycatenation framework formed by intermolecular hydrogen bonds and interlocking interactions is reported.

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The structure of a title novel one-dimensional ABX3-type organic–inorganic hybrid complex consists of benzyl­tri­ethyl­ammonium cations and one-dimensional anionic {[CdCl3]}n chains, in which the CdII centres are in an unusual two-layer five-coordinated arrangement.

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A one-dimensional polymeric structure of CoII with sulfadiazine and 1,3-bis­(pyridin-4-yl)propane is further stabilized by inter­molecular hydrogen bonding. The structure is of inter­est with respect to its electrochemical properties in the reduction reaction of H2O2 to H2O. Investigation of the thermal stability shows that the complex is stable up to 543 K.

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The title complex shows a prominent double-stranded ladder-like coordination polymer featuring square-pyramidal geometry around the two CuII centres.

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In a polymer of 2,5-bis­[4-methyl-3-(pyridin-3-yl)phen­yl]-1,3,4-oxa­diazole (L) with ZnCl2, one-dimensional P (plus) and M (minus) helical chains are formed, where the ligand has different directions of twist. The helical chains stack together via inter­chain π–π and C—H⋯π inter­actions.

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A one-dimensional coordination polymer with a twofold symmetric repeat unit containing three MnII centres. Two different coordination geometries are observed for the two independent MnII metal centres, viz. a distorted penta­gonal bipyramid and a distorted octa­hedron.

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The title compound comprises one-dimensional zigzag polymers of MgII cations bridged by isobutyrate groups. The crystal structure is characterized by stacks of hydro­phobic (isobutyrate) and hydro­philic (H2O) groups that alternate along the a axis.

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The structural evidence for the formation of a cluster-based chain-like polymeric structure incorporating both syn and anti conformers of a flexible dicarboxylate ligand is reported.

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A novel cadmium complex consists of one-dimensional ladders constructed from [Cd2(COO)2] dimeric subunits. A combination of hydrogen bonding and π–π stacking inter­actions extend the one-dimensional ladders into a three-dimensional supra­molecular architecture.

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A one-dimensional polymeric structure of CdII with sulfaquinoxaline is further stabilized by inter­molecular hydrogen bonding. The fluorescence spectrum reveals that the complex emits strong blue fluorescence. The thermal analysis shows that the framework is stable up to 663 K.

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A novel anionic tubular CdII coordination polymer based on the 5-(carboxyl­atometh­oxy)benzene-1,3-di­carboxyl­ate ligand and containing 4-amino­pyridinium cations had been synthesized under hydro­thermal conditions. In the solid state, the 4-amino­pyridinium cation props up the structure through hydrogen bonds to the O-atom acceptors of ligands and solvent water mol­ecules.

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A novel infinite one-dimensional coordination polymer involving N′-(2-hy­droxy­benzyl­idene)-2-(naphthalen-2-yl­oxy)aceto­hydrazide, and a trinuclear nickel complex of 2-hy­droxy-N′-(2-oxo-2-phen­oxy­ethyl)benzo­hydrazide with a one-dimensional network structure constructed by hydrogen-bonding inter­actions, are reported.





















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In the title compound, the Pb atom sits on a crystallographic C2 axis and is six-coordinate, ligated by two chelating carboxyl­ate groups from two 3-(pyridin-4-yl)benzoate ligands and by two N atoms from another two benzoate ligands. Each ligand is conformationally chiral and bridges two PbII centres, extending the structure into a corrugated two-dimensional (4,4) net.

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A rare two-dimensional organically templated halocadmate with a novel polymeric anion has been synthesized and characterized. It consists of tri­methyl­sulfonium cations sandwiched between layers of a two-dimensional μ2-chlorido-di-μ2-thio­cyanato-cadmate(II) polyanion.

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The title compound is a two-dimensional network containing an –Mn—O—C—O—Mn– chain. Each layer presents a herringbone pattern and interacts with neighbouring layers through intermolecular hydrogen bonds.

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The layered polymeric structure of a benzene-1,2,4,5-tetra­carboxyl­ate–Cu complex forms parallelogram-shaped channels.

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The co-deposition method was used for preparation of the mixed-valence supra­molecular compound {[CuI4(O2CCF3)4]2–{μ2-OC(CH3)2}2–[CuII2(O2CCF3)4]}, which consists of copper(I) and copper(II) tri­fluoro­acetate units held together by acetone bridges and inter­molecular Cu⋯O inter­actions.

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The coordination polymer [Cu(ptt)]n (ptt is 1-phenyl-1H-1,2,3,4-tetra­zole-5-thiol­ate) has been prepared under solvothermal conditions. Its structure features two-dimensional layers which lie parallel to the (100) plane.














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Reaction of a newly synthesized 3-(3,5-dicarboxybenzyloxy)benzoic acid ligand with zinc ions yielded a single-framework metal–organic coordination polymer (MOF) of attractive architecture.

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In the title coordination polymer, each AgI cation has a distorted tetra­hedral geometry coordinated by three of the four carboxyl­ate O atoms and the S atom from symmetry-related sulfane­di­yl­di­acetate ligands. The bridging sulfane­di­yl­di­acetate groups lead to a two-dimensional layer structure and the layers are interconnected via Ag—S bonds.

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The title AgI coordination polymer is a novel three-dimensional framework involving mixed naphthalene-1,5-disulfonate and aminoacetate ligands. In the crystal structure, each of the three different functional groups (carboxylate, amino and sulfonate) is coordinated to the AgI atoms.

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In a novel Cu–Na heteronuclear three-dimensional coordination polymer, the carboxyl­ate groups of iminodi­acetate (ida) ligands act as bridges and connect [Cu(ida)] and [Cu(ida)2] building blocks in a 2:1 ratio, forming two-dimensional arrays. These layers are inter­connected into a three-dimensional structure by sodium ions.

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A 4-(isonicotinamido)­phthalate ligand links NiII centres into a three-dimensional structure with sra topology. The structure is stabilized by N—H⋯O hydrogen bonding between uncoordinated amide groups and extensive O—H⋯O hydrogen bonding between the coordinated water mol­ecules.

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A three-dimensional metallohelicate is constructed from one-dimensional metal–organic helices of purine-containing 3-(6-oxo-6,9-di­hydro-1H-purin-1-yl)propionate ligands and zinc(II) ions.

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In a novel three-dimensional CdII complex prepared by hydro­thermal assembly of Cd(NO3)2·4H2O, 1,4-bis­[2-(pyridin-4-yl)ethenyl]benzene and 2,2′-(1,4-phenyl­ene)di­acetic acid, each CdII centre is located in a distorted penta­gonal bipyramidal coordination environment. The three-dimensional net can be regarded as a diamondoid network by treating the CdII atoms as nodes and the benzene and di­acetic acid ligands as linkers.

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A metal–organic framework (MOF) is reported in which an AgI cation is coordinated by two N atoms from two different 3,5-diethyl-1,2,4-triazolate ligands in a linear configuration. Each AgI cation is then connected to two adjacent AgI cations via a μ3-N1:N2:N4-triazolate ligand.

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Three-dimensional coordination polymers made up of lanthanides, oxydi­acetate and sulfate show novel structures in which the sulfate anion tends to reach saturation as a ligand.






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The central Na+ cation exhibits distorted octa­hedral coordination geometry involving two deprotonated O atoms, two hy­droxy O atoms and two double-bonded O atoms of the bis­phosphon­ate anion. Pairs of sodium-centred octa­hedra share edges and the pairs are in turn connected to each other by the biphosphon­ate anion to form a two-dimensional network parallel to the (001) plane.

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A three-dimensional polymeric potassium complex incorporating bridging water mol­ecules and 2,4-dicarb­oxy-5-sulfonato­benzoate ligands forms a one-dimensional inorganic chain with cage-like K4(SO3)2 repeat units. The chains are bridged by carb­oxy­lic acid groups to form a two-dimensional layer, and these layers are further linked by carboyxlate groups and benzene rings to generate a three-dimensional framework.

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Two novel inorganic–organic coordination polymers, based on NaI cations with semi-rigid V-shaped di­carboxyl­ate ligands, have been prepared and structurally characterized.

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The crystal structures of bis­(4-methyl­anilinium) and bis­(4-iodo­anilinium) penta­molybdates were determined using laboratory X-ray data and refined by total energy minimization methods. The obtained structures present alternating organic cation and inorganic polyanion layers bound by weak bonding (apart from ionic inter­actions).

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The hydrated sodium salt of 4-chloro-3-nitro­benzoic acid and the hydrated sodium and potassium salts of 2-amino-4-nitro­benzoic acid are stabilized by intra- and inter­molecular hydrogen bonding and strong π–π ring inter­actions. Na centres are linked through centrosymmetric four-membered duplex water bridges and through 18-membered duplex head-to-tail ligand bridges. Similar centrosymmetric bridges are found in the potassium salt.

Special and virtual issues

Acta Crystallographica Section C is planning special issues on

The Structural Chemistry of Homogeneous and Heterogeneous Catalysts

NMR Crystallography

Full details are available on the special issues page.

The latest virtual issue, featuring Coordination polymers and with an introduction by Len Barbour, was published in July 2014.

What are the 'most read' articles from the recent special issues?

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