Discrete and Polymeric Cu(II) Coordination Complexes with a Flexible bis-(pyridylpyrazole) Ligand: Structural Diversity and Unexpected Solvothermal Reactivity

2013 ◽  
Vol 66 (4) ◽  
pp. 401 ◽  
Author(s):  
Chris S. Hawes ◽  
Paul E. Kruger
Keyword(s):  
Coordination Polymer ◽  
Copper Complexes ◽  
Three Dimensional ◽  
Structural Diversity ◽  
Bidentate Ligand ◽  
Two Dimensional ◽  
Ligand Complex ◽  
Structural Characterisation ◽  
Concomitant Reduction ◽  
Pure Phases

Reported here is the synthesis and structural characterisation of five copper complexes derived from the bis-bidentate ligand 4,4′-methylenebis(1-(2-pyridyl)-3,5-dimethylpyrazole), L. Complex 1, [Cu2L(CH3COO)4(OH2)2]·6H2O, is a single stranded unsaturated helical species that forms a highly connected three-dimensional hydrogen-bonding network, whereas [Cu2L(NO3)4], 2, is a coordination polymer derived from [Cu2L] fragments linked together via bridging nitrate anions to yield undulating two-dimensional sheets with (6,3)-topology. Complexes 3, 4, and 5 co-crystallise within a single batch when L is reacted under solvothermal conditions with Cu(NO3)2·2.5H2O in acetonitrile, and each contains a co-ligand formed by either decomposition of the solvent or ligand. Complex 3, [Cu4(NO3)4(µ-CH3COO)2(µ-OH)2L2], forms an unusual discrete cyclic tetrameric species containing acetate co-ligands derived through acetonitrile hydrolysis; whereas complex 4, [CuL(C2O4)(NO3)], forms a one-dimensional coordination polymer containing bridging oxalate co-ligands, formed through hydrolysis and oxidation of acetonitrile. Complex 5, [Cu2L(µ-CN)2], is a two-dimensional coordination polymer with (6,3) topology where bridging between Cu(i) centres is furnished by cyanide co-ligands, suggesting a ligand decomposition pathway for its origin, and produced with concomitant reduction of the Cu(ii) starting reagent. Having initially obtained 3, 4, and 5 serendipitously each were then prepared as pure phases by careful adjustment and control of the reaction conditions (reactant stoichiometry, concentrations, and solvothermal temperature), details of which are discussed.

A two-dimensional CdII coordination polymer with 2,2′-(disulfanediyl)dibenzoate and 1,10-phenanthroline ligands

2014 ◽  
Vol 70 (5) ◽  
pp. 517-521
Author(s):  
Yu-Xiu Jin ◽  
Fang Yang ◽  
Li-Min Yuan ◽  
Chao-Guo Yan ◽  
Wen-Long Liu
Keyword(s):  
Coordination Polymer ◽  
Three Dimensional ◽  
Phen Ligand ◽  
Supramolecular Architecture ◽  
Two Dimensional ◽  
Asymmetric Unit ◽  
Π Interactions ◽  
Carboxylate Groups ◽  
Phenanthroline Ligand ◽  
Phenanthroline Ligands

In poly[[μ3-2,2′-(disulfanediyl)dibenzoato-κ5 O:O,O′:O′′,O′′′](1,10-phenanthroline-κ2 N,N′)cadmium(II)], [Cd(C14H8O4S2)(C12H8N2)] n , the asymmetric unit contains one CdII cation, one 2,2′-(disulfanediyl)dibenzoate anion (denoted dtdb2−) and one 1,10-phenanthroline ligand (denoted phen). Each CdII centre is seven-coordinated by five O atoms of bridging/chelating carboxylate groups from three dtdb2− ligands and by two N atoms from one phen ligand, forming a distorted pentagonal–bipyramidal geometry. The CdII cations are bridged by dtdb2− anions to give a two-dimensional (4,4) layer. The layers are stacked to generate a three-dimensional supramolecular architecture via a combination of aromatic C—H...π and π–π interactions. The thermogravimetric and luminescence properties of this compound were also investigated.

Poly[deca-μ2-cyanido-dicyanidobis(μ2-ethylenediamine)bis(ethylenediamine)tricadmium(II)dicobalt(III)]: a two-dimensional coordination polymer

2009 ◽  
Vol 65 (3) ◽  
pp. m118-m120
Author(s):  
Olha Sereda ◽  
Helen Stoeckli-Evans
Keyword(s):  
Coordination Polymer ◽  
Network Structure ◽  
General Position ◽  
Rotation Axis ◽  
Three Dimensional ◽  
The Other ◽  
Dimensional Structure ◽  
Two Dimensional ◽  
Asymmetric Unit ◽  
Dimensional Network

The title coordination polymer, [Cd3Co2(CN)12(C2H8N2)4]n, has an infinite two-dimensional network structure. The asymmetric unit is composed of two crystallographically independent CdIIatoms, one of which is located on a twofold rotation axis. There are two independent ethylenediamine (en) ligands, one of which bis-chelates to the Cd atom that sits in a general position, while the other bridges this Cd atom to that sitting on the twofold axis. The Cd atom located on the twofold rotation axis is linked to four equivalent CoIIIatomsviacyanide bridges, while the Cd atom that sits in a general position is connected to three equivalent CoIIIatomsviacyanide bridges. In this way, a series of trinuclear, tetranuclear and pentanuclear macrocycles are linked to form a two-dimensional network structure lying parallel to thebcplane. In the crystal structure, these two-dimensional networks are linkedviaN—H...N hydrogen bonds involving an en NH2H atom and a cyanide N atom, leading to the formation of a three-dimensional structure. This coordination polymer is only the second example involving a cyanometallate where the en ligand is present in both chelating and bridging coordination modes.

A new two-dimensional managnese(II) coordination polymer constructed by 2,2′-(1,2-phenylene)bis(1H-imidazole-4,5-dicarboxylate)

2018 ◽  
Vol 74 (5) ◽  
pp. 599-603 ◽  
Author(s):  
Yan-Ju Liu ◽  
Di Cheng ◽  
Ya-Xue Li ◽  
Xiang-Ru Meng ◽  
Huai-Xia Yang
Keyword(s):  
Solid State ◽  
Coordination Polymer ◽  
Three Dimensional ◽  
Dimensional Structure ◽  
Coordination Geometry ◽  
Two Dimensional ◽  
Carboxylate Ligands ◽  
Rich Variety ◽  
Distorted Octahedral ◽  
Solvothermal Conditions

In recent years, N-heterocyclic carboxylate ligands have attracted much interest in the preparation of new coordination polymers since they contain N-atom donors, as well as O-atom donors, and have a rich variety of coordination modes which can lead to polymers with intriguing structures and interesting properties. A new two-dimensional coordination polymer, namely poly[[μ3-2,2′-(1,2-phenylene)bis(4-carboxy-1H-imidazole-5-carboxylato)-κ6 O 4,N 3,N 3′,O 4′:O 5:O 5′]manganese(II)], [Mn(C16H8N4O8)] n or [Mn(H4Phbidc)] n , has been synthesized by the reaction of Mn(OAc)2·4H2O (OAc is acetate) with 2,2′-(1,2-phenylene)bis(1H-imidazole-4,5-dicarboxylic acid) (H6Phbidc) under solvothermal conditions. In the polymer, each MnII ion is six-coordinated by two N atoms from one H4Phbidc2− ligand and by four O atoms from three H4Phbidc2− ligands, forming a significantly distorted octahedral MnN2O4 coordination geometry. The MnII ions are linked by hexadentate H4Phbidc2− ligands, leading to a two-dimensional structure parallel to the ac plane. In the crystal, adjacent layers are further connected by N—H...O hydrogen bonds, forming a three-dimensional structure in the solid state.

scholarly journals Structural diversity induced by ligand geometry: From two-dimensional to three-dimensional coordination polymers with pyridine

2020 ◽  
pp. 174751982096816
Author(s):  
Fang-Kuo Wang ◽  
Shi-Yao Yang ◽  
Hua-Ze Dong
Keyword(s):  
Coordination Polymers ◽  
Three Dimensional ◽  
Structural Diversity ◽  
Dimensional Structure ◽  
Layer By Layer ◽  
Two Dimensional ◽  
Guest Molecules ◽  
X Ray ◽  
Benzenedicarboxylic Acid ◽  
Benzenetricarboxylic Acid

Two coordination polymers with two-dimensional and three-dimensional structures are, {[Zn3(bdc)3(py)2]·2NMP}n (1) (H2bdc = 1,4-benzenedicarboxylic acid) and [Zn2(NO3−)(btc)(nmp)2(py)]n (2) (H3btc = 1,3,5-benzenetricarboxylic acid), synthesized by hot-solution reactions of Zn(NO3)2·6H2O, pyridine (py) and two different ligands in N-methylpyrrolidone (NMP). {[Zn3(bdc)3(py)2]·2NMP}n exhibits two-dimensional networks with trizinc subunits [Zn3(COO)6py2] stacking with a layer-by-layer alignment, and there are strong π–π interactions involving py from adjacent layers. [Zn2(NO3−)(btc)(nmp)2(py)]n has a three-dimensional structure containing two independent zinc ions, tetrahedral ZnO4 and octahedral ZnNO5. Based on X-ray studies, the coordination polymers {[Zn3(bdc)3(py)2]·2NMP}n (1) have a porous structure with NMP guest molecules. In contrast, X-ray studies revealed that coordination polymer [Zn2(NO3−)(btc)(nmp)2(py)]n (2) had a larger void that was inhabited by coordinated py and NMP. In addition, the form of the two coordination polymers changed from two-dimensional to three-dimensional with transformation of the ligand geometry.

Two dimensional stair-shaped coordination polymer exhibiting three-dimensional structure with cavities

2000 ◽  
pp. 717-718 ◽  
Author(s):  
Lei Zhang ◽  
Peng Cheng ◽  
Liang-Fu Tang ◽  
Zong-Hui Jiang ◽  
Dai-Zheng Liao ◽  
...  
Keyword(s):  
Coordination Polymer ◽  
Three Dimensional ◽  
Dimensional Structure ◽  
Two Dimensional ◽  
Three Dimensional Structure

[Ni(cyclam)(OCOR)2], a finite molecular complex: hydrogen-bonded supramolecular aggregation in one, two and three dimensions, and coordination polymers in one and two dimensions

2001 ◽  
Vol 58 (1) ◽  
pp. 78-93 ◽  
Author(s):  
Choudhury M. Zakaria ◽  
George Ferguson ◽  
Alan J. Lough ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bonding ◽  
Coordination Polymer ◽  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Two Dimensions ◽  
Three Dimensions ◽  
Two Dimensional ◽  
Compound I ◽  
Supramolecular Aggregation ◽  
Linear Coordination

In the complexes [Ni(cyclam)(OCOR)2] (cyclam = 1,4,8,11-tetraazacyclotetradecane), where (RCOO)− is 2-naphtho-ate [bis-(2-naphthoato)-1,4,8,11-tetraazacyclotetradecanenickel(II), (I), monoclinic P21/c, Z′ = 0.5], 3,5-dinitrobenzoate [bis-(3,5-dinitrobenzoato)-1,4,8,11-tetraazacyclotetradecanenickel(II), (II), triclinic P\bar 1, Z′ = 0.5], 4-nitrobenzoate [bis-(4-nitrobenzoato)-1,4,8,11-tetraazacyclotetradecanenickel(II), (III), monoclinic P21/n, Z′ = 0.5], 3-hydroxybenzoate [bis-(3-hydroxybenzoato)-1,4,8,11-tetraazacyclotetradecanenickel(II), (IV), monoclinic P21/c, Z′ = 0.5] and 4-aminobenzo-ate [bis-(4-aminobenzoato)-1,4,8,11-tetraazacyclotetradecanenickel(II), (V), monoclinic C2/c, Z′ = 0.5], the Ni lies on a centre of inversion with monodentate carboxylato ligands occupying trans sites. Compound (I) consists of isolated molecules. In (II) and (III), N—H...O hydrogen bonds link the complexes into chains. Compounds (IV) and (III) form two- and three-dimensional structures generated entirely by hard hydrogen bonds. The 5-hydroxyisophthalate(2−) anion forms a hydrated complex, [Ni(cyclam)(5-hydroxyisophthalate)(H2O)]·4H2O {[aqua-(5-hydroxyisophthalato)-1,4,8,11-tetraazacyclotetradecanenickel(II)] tetrahydrate, (VI), monoclinic Cc, Z′ = 1}, in which the monodentate carboxylato ligand and a water molecule occupy trans sites at Ni: extensive hydrogen bonding links the molecular aggregates into a three-dimensional framework. The terephthalate(2−) anion forms a hydrated linear coordination polymer {catena-poly[terephthalato-1,4,8,11-tetraazacyclotetradecanenickel(II)] monohydrate, (VII), monoclinic C2/c, Z′ = 0.5}. In 1,2,4,5-benzenecarboxylate tris[1,4,8,11-tetraazacyclotetradecanenickel(II)] diperchlorate hydrate (VIII), [Ni(cyclam)]3·[1,2,4,5-benzenetetracarboxylate(4−)]·[ClO4]2·-[H2O]3, there are two distinct Ni sites: [Ni(cyclam)]2+ and centrosymmetric [C10H2O8]4− units form a two-dimensional coordination polymer, whose sheets are linked by centrosymmetric [Ni(cyclam)(H2O)2]2+ cations.

scholarly journals Crystal structure of poly[μ2-aqua-aqua(μ2-4-nitro-2,5,6-trioxo-1,2,5,6-tetrahydropyridin-3-olato)hemi-μ4-oxalato-barium(II)]

2015 ◽  
Vol 71 (5) ◽  
pp. 459-462 ◽  
Author(s):  
Rusul Alabada ◽  
Olga Kovalchukova ◽  
Irina Polyakova ◽  
Svetlana Strashnova ◽  
Vladimir Sergienko
Keyword(s):  
Crystal Structure ◽  
Coordination Polymer ◽  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Water Molecules ◽  
Two Dimensional ◽  
Supramolecular Framework ◽  
Screw Axis ◽  
Bond Lengths ◽  
Chelate Rings

In the title coordination polymer, [Ba(C5HN2O6)(C2O4)0.5(H2O)2]n, the tenfold coordination of the Ba centre consists of four O atoms from the two 4-nitro-2,5,6-trioxo-1,2,5,6-tetrahydropyridin-3-olate (L) anions, three O atoms of two oxalate anions and three water molecules. The Ba—O bond lengths fall in the range 2.698 (3)–2.978 (3) Å. TheLligand chelates two Ba atoms related by a screw axis, leading to formation of fused five- and six-membered chelate rings. Due to the bridging function of the ligands and water molecules, the complex monomers are connected into polymeric two-dimensional layers parallel to thebcplane. Intermolecular O—H...O hydrogen bonds link these layers into a three-dimensional supramolecular framework.

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