Two cobalt(II) supramolecular isomers based on N,N′‐bis(pyridin‐3‐yl)oxalamide induced by the molecular orientation of lattice DMF molecules

Supramolecular isomerism for coordination networks refers to the existence of different architectures having the same building blocks and identical stoichiometries. For a given building block, different arrangements can lead to the formation of a series of supramolecular isomers. Two one‐dimensional Co^II coordination polymers based on N,N′‐bis(pyridin‐3‐yl)oxalamide (BPO), both catena‐poly[[[dichloridocobalt(II)]‐bis[μ‐N,N′‐bis(pyridin‐3‐yl)oxalamide‐κ²N:N′]] dimethylformamide disolvate], {[CoCl₂(C₁₂H₁₀N₄O₂)₂]·2C₃H₇NO}_n, have been assembled by the solvothermal method. Single‐crystal X‐ray diffraction analyses reveal that the two compounds are supramolecular isomers, the isomerism being induced by the orientation of the dimethylformamide (DMF) molecules in the crystal lattice.     

Three novel topologically different metal–organic frameworks built from 3‐nitro‐4‐(pyridin‐4‐yl)benzoic acid

The design and synthesis of metal–organic frameworks (MOFs) have attracted much interest due to the intriguing diversity of their architectures and topologies. However, building MOFs with different topological structures from the same ligand is still a challenge. Using 3‐nitro‐4‐(pyridin‐4‐yl)benzoic acid (HL) as a new ligand, three novel MOFs, namely poly[[(N,N‐dimethylformamide‐κO)bis[μ₂‐3‐nitro‐4‐(pyridin‐4‐yl)benzoato‐κ³O,O′:N]cadmium(II)] N,N‐dimethylformamide monosolvate methanol monosolvate], {[Cd(C₁₂H₇N₂O₄)₂(C₃H₇NO)]·C₃H₇NO·CH₃OH}_n, ( 1 ), poly[[(μ₂‐acetato‐κ²O:O′)[μ₃‐3‐nitro‐4‐(pyridin‐4‐yl)benzoato‐κ³O:O′:N]bis[μ₃‐3‐nitro‐4‐(pyridin‐4‐yl)benzoato‐κ⁴O,O′:O′:N]dicadmium(II)] N,N‐dimethylacetamide disolvate monohydrate], {[Cd₂(C₁₂H₇N₂O₄)₃(CH₃CO₂)]·2C₄H₉NO·H₂O}_n, ( 2 ), and catena‐poly[[[diaquanickel(II)]‐bis[μ₂‐3‐nitro‐4‐(pyridin‐4‐yl)benzoato‐κ²O:N]] N,N‐dimethylacetamide disolvate], {[Ni(C₁₂H₇N₂O₄)₂(H₂O)₂]·2C₄H₉NO}_n, ( 3 ), have been prepared. Single‐crystal structure analysis shows that the Cd^II atom in MOF ( 1 ) has a distorted pentagonal bipyramidal [CdN₂O₅] coordination geometry. The [CdN₂O₅] units as 4‐connected nodes are interconnected by L^? ligands to form a fourfold interpenetrating three‐dimensional (3D) framework with a dia topology. In MOF ( 2 ), there are two crystallographically different Cd^II ions showing a distorted pentagonal bipyramidal [CdNO₆] and a distorted octahedral [CdN₂O₄] coordination geometry, respectively. Two Cd^II ions are connected by three carboxylate groups to form a binuclear [Cd₂(COO)₃] cluster. Each binuclear cluster as a 6‐connected node is further linked by acetate groups and L^? ligands to produce a non‐interpenetrating 3D framework with a pcu topology. MOF ( 3 ) contains two crystallographically distinct Ni^II ions on special positions. Each Ni^II ion adopts an elongated octahedral [NiN₂O₄] geometry. Each Ni^II ion as a 4‐connected node is linked by L^? ligands to generate a two‐dimensional network with an sql topology, which is further stabilized by two types of intermolecular OW—HW…O hydrogen bonds to form a 3D supramolecular framework. MOFs ( 1 )–( 3 ) were also characterized by powder X‐ray diffraction, IR spectroscopy and thermogravimetic analysis. Furthermore, the solid‐state photoluminescence of HL and MOFs ( 1 ) and ( 2 ) have been investigated. The photoluminescence of MOFs ( 1 ) and ( 2 ) are enhanced and red‐shifted with respect to free HL. The gas adsorption investigation of MOF ( 2 ) indicates a good separation selectivity (71) of CO₂/N₂ at 273 K (i.e. the amount of CO₂ adsorption is 71 times higher than N₂ at the same pressure).     

ZnII and CuII complexes generated from 5‐(pyridin‐4‐yl)‐3‐[2‐(pyridin‐4‐yl)ethyl]‐1,3,4‐oxadiazole‐2(3H)‐thione

A new 1,3,4‐oxadiazole‐containing bispyridyl ligand, namely 5‐(pyridin‐4‐yl)‐3‐[2‐(pyridin‐4‐yl)ethyl]‐1,3,4‐oxadiazole‐2(3H)‐thione (L), has been used to create the novel complexes tetranitratobis{μ‐5‐(pyridin‐4‐yl)‐3‐[2‐(pyridin‐4‐yl)ethyl]‐1,3,4‐oxadiazole‐2(3H)‐thione}zinc(II), [Zn₂(NO₃)₄(C₁₄H₁₂N₄OS)₂], (I), and catena‐poly[[[dinitratocopper(II)]‐bis{μ‐5‐(pyridin‐4‐yl)‐3‐[2‐(pyridin‐4‐yl)ethyl]‐1,3,4‐oxadiazole‐2(3H)‐thione}] nitrate acetonitrile sesquisolvate dichloromethane sesquisolvate], {[Cu(NO₃)(C₁₄H₁₂N₄OS)₂]NO₃·1.5CH₃CN·1.5CH₂Cl₂}_n, (II). Compound (I) presents a distorted rectangular centrosymmetric Zn₂L₂ ring (dimensions 9.56 × 7.06 Å), where each Zn^II centre lies in a {ZnN₂O₄} coordination environment. These binuclear zinc metallocycles are linked into a two‐dimensional network through nonclassical C—H...O hydrogen bonds. The resulting sheets lie parallel to the ac plane. Compound (II), which crystallizes as a nonmerohedral twin, is a coordination polymer with double chains of Cu^II centres linked by bridging L ligands, propagating parallel to the crystallographic a axis. The Cu^II centres adopt a distorted square‐pyramidal CuN₄O coordination environment with apical O atoms. The chains in (II) are interlinked via two kinds of π–π stacking interactions along [01]. In addition, the structure of (II) contains channels parallel to the crystallographic a direction. The guest components in these channels consist of dichloromethane and acetonitrile solvent molecules and uncoordinated nitrate anions.     

Three AgI,CuI and CdII coordination polymers based on the new asymmetrical ligand 2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole: syntheses,characterization and emission properties

The new asymmetrical organic ligand 2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole ( L , C₁₇H₁₃N₅O), containing pyridine and imidazole terminal groups, as well as potential oxdiazole coordination sites, was designed and synthesized. The coordination chemistry of L with soft Ag^I, Cu^I and Cd^II metal ions was investigated and three new coordination polymers (CPs), namely, catena‐poly[[silver(I)‐μ‐2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole] hexafluoridophosphate], {[Ag( L )]PF₆}_n, catena‐poly[[copper(I)‐di‐μ‐iodido‐copper(I)‐bis(μ‐2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole)] 1,4‐dioxane monosolvate], {[Cu₂I₂( L )₂]·C₄H₈O₂}_n, and catena‐poly[[[dinitratocopper(II)]‐bis(μ‐2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole)]–methanol–water (1/1/0.65)], {[Cd( L )₂(NO₃)₂]·2CH₄O·0.65H₂O}_n, were obtained. The experimental results show that ligand L coordinates easily with linear Ag^I, tetrahedral Cu^I and octahedral Cd^II metal atoms to form one‐dimensional polymeric structures. The intermediate oxadiazole ring does not participate in the coordination interactions with the metal ions. In all three CPs, weak π–π interactions between the nearly coplanar pyridine, oxadiazole and benzene rings play an important role in the packing of the polymeric chains.     

A new one‐dimensional CdII coordination polymer with a two‐dimensional layered structure incorporating 2‐[(1H‐imidazol‐1‐yl)methyl]‐1H‐benzimidazole and benzene‐1,2‐dicarboxylate ligands

The N‐heterocyclic ligand 2‐[(1H‐imidazol‐1‐yl)methyl]‐1H‐benzimidazole (imb) has a rich variety of coordination modes and can lead to polymers with intriguing structures and interesting properties. In the coordination polymer catena‐poly[[cadmium(II)‐bis[μ‐benzene‐1,2‐dicarboxylato‐κ⁴O¹,O^1′:O²,O^2′]‐cadmium(II)‐bis{μ‐2‐[(1H‐imidazol‐1‐yl)methyl]‐1H‐benzimidazole}‐κ²N²:N³;κ²N³:N²] dimethylformamide disolvate], {[Cd(C₈H₄O₄)(C₁₁H₁₀N₄)]·C₃H₇NO}_n, (I), each Cd^II ion exhibits an irregular octahedral CdO₄N₂ coordination geometry and is coordinated by four O atoms from two symmetry‐related benzene‐1,2‐dicarboxylate (1,2‐bdic²⁻) ligands and two N atoms from two symmetry‐related imb ligands. Two Cd^II ions are connected by two benzene‐1,2‐dicarboxylate ligands to generate a binuclear [Cd₂(1,2‐bdic)₂] unit. The binuclear units are further connected into a one‐dimensional chain by pairs of bridging imb ligands. These one‐dimensional chains are further connected through N—H…O hydrogen bonds and π–π interactions, leading to a two‐dimensional layered structure. The dimethylformamide solvent molecules are organized in dimeric pairs via weak interactions. In addition, the title polymer exhibits good fluorescence properties in the solid state at room temperature.     

Four‐ and five‐coordinate copper(II) complexes with N‐(4,4‐diphenyl‐5‐oxo‐4,5‐dihydro‐1H‐imidazol‐2‐yl)glycine

The two title mononuclear compounds are four‐coordinate bis[N‐(5‐oxo‐4,4‐diphenyl‐4,5‐dihydro‐1H‐imidazolidin‐2‐ylidene)glycinato]copper(II) dimethylformamide disolvate, [Cu(C₁₇H₁₄N₃O₃)₂]·2C₃H₇NO, (I), and five‐coordinate aquabis[N‐(5‐oxo‐4,4‐diphenyl‐4,5‐dihydro‐1H‐imidazolidin‐2‐ylidene)glycinato]copper(II) dimethylformamide disolvate, [Cu(C₁₇H₁₄N₃O₃)₂(H₂O)]·2C₃H₇NO, (II). In (I), the Cu^II ion lies on an inversion centre with one‐half of the complex molecule in the asymmetric unit, while in (II) there are two independent ligand molecules in the asymmetric unit, with the Cu^II ion and coordinated water molecule located on a general position. In both crystal structures, the complex molecules assemble in ribbons via N—H...O hydrogen‐bond networks.     

Temperature‐induced solid‐to‐solid transformation in helical homochiral coordination polymers

The reactions of (R)‐ and (S)‐4‐(1‐carboxyethoxy)benzoic acid (H₂CBA) with 1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene (1,3‐BMIB) ligands afforded a pair of homochiral coordination polymers (CPs), namely, poly[[[μ‐1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene][μ‐(S)‐4‐(1‐carboxylatoethoxy)benzoato]zinc(II)] monohydrate], {[Zn(C₁₀H₈O₅)(C₁₄H₁₄N₄)]·H₂O}_n or {[Zn{(S)‐CBA}(1,3‐BMIB)]·H₂O}_n ( 1‐L ), and poly[[[μ‐1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene][μ‐(R)‐4‐(1‐carboxylatoethoxy)benzoato]zinc(II)] monohydrate] ( 1‐D ). Three kinds of helical chains exist in compounds 1‐D and 1‐L , which are constructed from Zn^II atoms, 1,3‐BMIB ligands and/or CBA^2? ligands. When the as‐synthesized crystals of 1‐L and 1‐D were further heated in the mother liquor or air, poly[[μ‐1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene][μ‐(S)‐4‐(1‐carboxylatoethoxy)benzoato]zinc(II)], [Zn(C₁₀H₈O₅)(C₁₄H₁₄N₄)]_n or [Zn{(S)‐CBA}(1,3‐BMIB)]_n ( 2‐L ), and poly[[μ‐1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene][μ‐(R)‐4‐(1‐carboxylatoethoxy)benzoato]zinc(II)] ( 2‐D ) were obtained, respectively. The single‐crystal structure analysis revealed that 2‐L and 2‐D only contained one type of helical chain formed by Zn^II atoms and 1,3‐BMIB and CBA^2? ligands, which indicated that the helical chains were reconstructed though solid‐to‐solid transformation. This result not only means the realization of helical transformation, but also gives a feasible strategy to build homochiral CPs.     

Di‐μ‐hydroxido‐bis{[bis(6‐methyl‐2‐pyridylmethyl)(2‐phenylethyl)amine‐κ3N′,N′′,N′′′]copper(II)} bis(perchlorate)

The title compund, [Cu₂(OH)₂(C₂₂H₂₅N₃)₂](ClO₄)₂, is a copper(II) dimer, with two [CuL]²⁺ units [L is bis(6‐methyl‐2‐pyridylmethyl)(2‐phenylethyl)amine] bridged by hydroxide groups to define the {[CuL](μ‐OH)₂[CuL]}²⁺ cation. Charge balance is provided by perchlorate counter‐anions. The cation has a crystallographic inversion centre halfway between the Cu^II ions, which are separated by 3.0161 (8) Å. The central core of the cation is an almost regular Cu₂O₂ parallelogram of sides 1.931 (2) and 1.935 (2) Å, with a Cu—O—Cu angle of 102.55 (11)°. The coordination geometry around each Cu^II centre can be best described as a square‐based pyramid, with three N atoms from L ligands and two hydroxide O atoms completing the coordination environment. Each cationic unit is hydrogen bonded to two perchlorate anions by means of hydroxide–perchlorate O—H...O interactions.     

A one‐dimensional lead(II) coordination polymer with terminal and bridging 5‐carboxy‐2‐(pyridin‐3‐yl)‐1H‐imidazole‐4‐carboxylate ligands

In the coordination polymer catena‐poly[[[diaqua[5‐carboxy‐2‐(pyridin‐3‐yl)‐1H‐imidazole‐4‐carboxylato‐κ²N³,O⁴]lead(II)]‐μ‐5‐carboxy‐2‐(pyridin‐3‐yl)‐1H‐imidazole‐4‐carboxylato‐κ³N³,O⁴:N²] dihydrate], {[Pb(C₁₀H₆N₃O₄)(H₂O)₂]·2H₂O}_n, the two 5‐carboxy‐2‐(pyridin‐3‐yl)‐1H‐imidazole‐4‐carboxylate ligands have different coordination modes, one being terminal and the other bridging. The bridging ligand links Pb^II cations into one‐dimensional coordination polymer chains. The structure is also stabilized by intra‐ and interchain π–π stacking interactions between the pyridine rings, resulting in the formation of a two‐dimensional network. Extensive hydrogen‐bonding interactions lead to the formation of a three‐dimensional supramolecular network.     

A two‐dimensional copper(II) coordination polymer based on 2,4′‐oxybis(benzoate) and 4,4′‐bipyridine

The reaction of Cu(NO₃)₂·3H₂O with 2,4′‐oxybis(benzoic acid) and 4,4′‐bipyridine under hydrothermal conditions produced a new mixed‐ligand two‐dimensional copper(II) coordination polymer, namely poly[[(μ‐4,4′‐bipyridine‐κ²N ,N ′)[μ‐2,4′‐oxybis(benzoato)‐κ⁴O ²,O ^2′:O ⁴,O ^4′]copper(II)] monohydrate], {[Cu(C₁₄H₈O₅)(C₁₀H₈N₂)]·H₂O}_n , which was characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single‐crystal X‐ray diffraction. The X‐ray diffraction crystal structure analysis reveals that the Cu^II ions are connected to form a two‐dimensional wave‐like network through 4,4′‐bipyridine and 2,4′‐oxybis(benzoate) ligands. The two‐dimensional layers are expanded into a three‐dimensional supramolecular structure through intermolecular O—H…O and C—H…O hydrogen bonds. Furthermore, magnetic susceptibility measurements indicate that the complex shows weak antiferromagnetic interactions between adjacent Cu^II ions.     

Dimeric copper(II) trimethylsilyl­acetate adducts with pyridine, 2‐­methylpyridine, 3‐methylpyridine and quinoline,and a polymeric copper(II) trimethylsilylacetate

In the crystals of bis(pyridine‐N)tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II), [Cu₂(C₅H₁₁O₂Si)₄(C₅H₅N)₂], (I), the dinuclear Cu^II complexes have cage structures with Cu?Cu distances of 2.632 (1) and 2.635 (1) Å. In the crystals of bis(2‐­methylpyridine‐N)tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II), [Cu₂(C₅H₁₁O₂Si)₄(C₆H₇N)₂], (II), bis­(3‐methylpyridine‐N)tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II), [Cu₂(C₅H₁₁O₂Si)₄(C₆H₇N)₂], (III), and bis(quinoline‐N)­tetrakis(μ‐­trimethylsilylacetato‐O:O′)dicopper(II), [Cu₂(C₅H₁₁O₂Si)₄(C₉H₇N)₂], (IV), the centrosymmetric dinuclear Cu^II complexes have a cage structure with Cu?Cu distances of 2.664 (1), 2.638 (3) and 2.665 (1) Å, respectively. In the crystals of catena‐poly­[tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II)], [Cu₂(C₅H₁₁O₂Si)₄]_n, (V), the dinuclear Cu^II units of a cage structure are linked by the cyclic Cu—O bonds at the apical positions to form a linear chain by use of a glide translation.     

A self‐penetrated three‐dimensional zinc(II) coordination framework based on 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzoic acid and 1,3‐bis[(imidazol‐1‐yl)methyl]benzene ligands: synthesis,structure and properties

With the rapid development of metal–organic frameworks (MOFs), a variety of MOFs and their derivatives have been synthesized and reported in recent years. Commonly, multifunctional aromatic polycarboxylic acids and nitrogen‐containing ligands are employed to construct MOFs with fascinating structures. 4,4′,4′′‐(1,3,5‐Triazine‐2,4,6‐triyl)tribenzoic acid (H₃TATB) and the bidentate nitrogen‐containing ligand 1,3‐bis[(imidazol‐1‐yl)methyl]benzene (bib) were selected to prepare a novel Zn^II‐MOF under solvothermal conditions, namely poly[[tris{μ‐1,3‐bis[(imidazol‐1‐yl)methyl]benzene}bis[μ₃‐4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzoato]trizinc(II)] dimethylformamide disolvate trihydrate], {[Zn₃(C₂₄H₁₂N₃O₆)₂(C₁₄H₁₄N₄)₃]·2C₃H₇NO·3H₂O}_n ( 1 ). The structure of 1 was characterized by single‐crystal X‐ray diffraction, IR spectroscopy and powder X‐ray diffraction. The properties of 1 were investigated by thermogravimetric and fluorescence analysis. Single‐crystal X‐ray diffraction shows that 1 belongs to the monoclinic space group Pc. The asymmetric unit contains three crystallographically independent Zn^II centres, two 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzoate (TATB^3?) anions, three complete bib ligands, one and a half free dimethylformamide molecules and three guest water molecules. Each Zn^II centre is four‐coordinated and displays a distorted tetrahedral coordination geometry. The Zn^II centres are connected by TATB^3? anions to form an angled ladder chain with large windows. Simultaneously, the bib ligands link Zn^II centres to give a helical Zn–bib–Zn chain. Furthermore, adjacent ladders are bridged by Zn–bib–Zn chains to form a fascinating three‐dimensional self‐penetrated framework with the short Schläfli symbol 6⁵·7·8¹³·9·10. In addition, the luminescence properties of 1 in the solid state and the fluorescence sensing of metal ions in suspension were studied. Significantly, compound 1 shows potential application as a fluorescent sensor with sensing properties for Zr⁴⁺ and Cu²⁺ ions.     

Two different one‐dimensional supramolecular chains formed from the reaction of 2‐[1‐(pyridin‐4‐ylmethyl)‐1H‐benzimidazol‐2‐yl]quinoline with two different precursors,Co(NO3)2 and CoCl2

Two different one‐dimensional supramolecular chains with Co^II cations have been synthesized based on the semi‐rigid ligand 2‐[1‐(pyridin‐4‐ylmethyl)‐1H‐benzimidazol‐2‐yl]quinoline (L), obtained by condensation of 2‐(1H‐benzimidazol‐2‐yl)quinoline and 4‐(chloromethyl)pyridine hydrochloride. Starting from different Co^II salts, two new compounds have been obtained, viz. catena‐poly[[[dinitratocobalt(II)]‐μ‐2‐[1‐(pyridin‐4‐ylmethyl)‐1H‐benzimidazol‐2‐yl]quinoline] dichloromethane monosolvate acetonitrile monosolvate], {[Co(NO₃)₂(C₂₂H₁₆N₄)]·CH₂Cl₂·CH₃CN}_n, (I) and catena‐poly[[[dichloridocobalt(II)]‐μ‐2‐[1‐(pyridin‐4‐ylmethyl)‐1H‐benzimidazol‐2‐yl]quinoline] methanol disolvate], {[CoCl₂(C₂₂H₁₆N₄)]·2CH₃OH}_n, (II). In (I), the Co^II centres lie in a distorted octahedral [CoN₃O₃] coordination environment. {Co(NO₃)₂L}_n units form one‐dimensional helical chains, where the L ligand has different directions of twist. The helical chains stack together via interchain π–π interactions to form a two‐dimensional sheet, and another type of π–π interaction further connects neighbouring sheets into a three‐dimensional framework with hexagonal channels, in which the acetonitrile molecules and disordered dichloromethane molecules are located. In (II), the Co^II centres lie in a distorted trigonal–bipyramidal [CoCl₂N₃] coordination environment. {CoCl₂L}_n units form one‐dimensional chains. The chains interact via C—H...π and C—H...Cl interactions. The result is that two‐dimensional sheets are generated, which are further linked into a three‐dimensional framework via interlayer C—H...Cl interactions. When viewed down the crystallographic b axis, the methanol solvent molecules are located in an orderly manner in wave‐like channels.     

A new copper(II) supramolecular coordination polymer and a dinuclear compound with multifunctional 2‐amino‐5‐sulfobenzoic acid and flexible N‐donor ligands: synthesis,structure and characterization

Multifunctional 2‐amino‐5‐sulfobenzoic acid (H₂afsb) can exhibit a variety of roles during the construction of supramolecular coordination polymers. The pendant carboxylic acid, sulfonic acid and amino groups could not only play a role in directing bonding but could also have the potential to act as hydrogen‐bond donors and acceptors, resulting in extended high‐dimensional supramolecular networks. Two new Cu^II coordination compounds, namely catena‐poly[[[diaquacopper(II)]‐μ‐1,6‐bis(1H‐1,2,4‐triazol‐1‐yl)hexane‐κ²N⁴:N^4′] bis(3‐amino‐4‐carboxybenzenesulfonate) dihydrate], {[Cu(C₁₀H₁₆N₆)₂(H₂O)₂](C₇H₆NO₅S)₂·2H₂O}_n or {[Cu(bth)₂(H₂O)₂](Hafsb)₂·2H₂O}_n, (1), and bis(μ‐2‐amino‐5‐sulfonatobenzoato‐κ²O¹:O^1′)bis{μ‐1,2‐bis[(1H‐imidazol‐1‐yl)methyl]benzene‐κ²N³:N^3′}bis[aquacopper(II)] trihydrate, [Cu₂(C₇H₅NO₅S)₂(C₁₄H₁₄N₄)₂(H₂O)₂]·3H₂O or [Cu₂(afsb)₂(obix)₂(H₂O)₂]·3H₂O, (2), have been obtained through the assembly between H₂afsb and the Cu^II ion in the presence of the flexible N‐donor ligands 1,6‐bis(1H‐1,2,4‐triazol‐1‐yl)hexane (bth) and 1,2‐bis[(1H‐1,2,4‐triazol‐1‐yl)methyl]benzene (obix), respectively. Compound (1) consists of a cationic coordination polymeric chain and 3‐amino‐4‐carboxybenzenesulfonate (Hafsb⁻) anions. Compound (2) exhibits an asymmetric dinuclear structure. There are hydrogen‐bonded networks within the lattices of (1) and (2). Interestingly, both (1) and (2) exhibit reversible dehydration–rehydration behaviour.     

Bis(μ‐2‐{5‐[(pyridin‐4‐ylmethyl)sulfanyl]‐1,3,4‐oxadiazol‐2‐yl}phenolato)bis[(acetylacetonato)copper(II)]: a novel binuclear metallocycle

The new asymmetric ligand 2‐{5‐[(pyridin‐4‐ylmethyl)sulfanyl]‐1,3,4‐oxadiazol‐3‐yl}phenol (HL) has been used to synthesize the novel discrete title binuclear metallocycle, [Cu₂(C₁₄H₁₀N₃O₂S)₂(C₅H₇O₂)₂] or Cu₂L₂(acac)₂ (acac is acetylacetonate). Each Cu^II centre is five‐coordinate and adopts a square‐pyramidal geometry. Two ligands are connected by two Cu^II cations to form the dinuclear metallocycle, which lies across a crystallographic inversion centre. Discrete molecules are linked into a two‐dimensional structure through weak Cu...S, C—H...π and π–π interactions.     

Binuclear and chain‐structure zinc(II) complexes constructed from 3,4‐dimethoxy‐trans‐cinnamic acid and N‐donor coligands 4‐(1H‐pyrazol‐3‐yl)pyridine and 4,4′‐bipyridine

3,4‐Dimethoxy‐trans‐cinnamic acid (Dmca) reacts with zinc sulfate in the presence of 4‐(1H‐pyrazol‐3‐yl)pyridine (L₁) or 4,4′‐bipyridine (L₂) under hydrothermal conditions to afford two mixed‐ligand coordination complexes, namely tetrakis(μ‐3,4‐dimethoxy‐trans‐cinnamato‐κ²O:O′)bis[[4‐(1H‐pyrazol‐3‐yl)pyridine]zinc(II)] heptahydrate, [Zn₂(C₁₁H₁₁O₄)₄(C₈H₇N₃)₂]·7H₂O or [Zn₂(Dmca)₄(L₁)₂]·7H₂O, (I), and catena‐poly[[bis(3,4‐dimethoxy‐trans‐cinnamato‐κO)zinc(II)]‐μ‐4,4′‐bipyridine‐κ²N:N′], [Zn(C₁₁H₁₁O₄)₂(C₁₀H₈N₂)]_n or [Zn(Dmca)₂(L₂)]_n, (II). The Zn^II centres in the two compounds display different coordination polyhedra. In complex (I), the Zn^II cation is five‐coordinated with a pseudo‐square‐pyramidal geometry, while in complex (II) the Zn^II cation sits on a twofold axis and adopts a distorted tetrahedral coordination environment. Complex (I) features a centrosymmetric binuclear paddle‐wheel‐like structure, while complex (II) shows a chain structure. This study emphasizes the significant effect of the coordination mode of both carboxylate‐group and N‐donor coligands on the formation of complex structures.     

The effect of the coordination orientation of N atoms on polymeric structures: synthesis and characterization of one‐ and two‐dimensional CuII coordination polymers based on 4‐amino‐3‐(pyridin‐2‐yl)‐5‐[(pyridin‐3‐ylmethyl)sulfanyl]‐1,2,4‐triazole

Three new one‐ (1D) and two‐dimensional (2D) Cu^II coordination polymers, namely poly[[bis{μ₂‐4‐amino‐3‐(pyridin‐2‐yl)‐5‐[(pyridin‐3‐ylmethyl)sulfanyl]‐1,2,4‐triazole}copper(II)] bis(methanesulfonate) tetrahydrate], {[Cu(C₁₃H₁₂N₅S)₂](CH₃SO₃)₂·4H₂O}_n ( 1 ), catena‐poly[[copper(II)‐bis{μ₂‐4‐amino‐3‐(pyridin‐2‐yl)‐5‐[(pyridin‐4‐ylmethyl)sulfanyl]‐1,2,4‐triazole}] dinitrate methanol disolvate], {[Cu(C₁₃H₁₂N₅S)₂](NO₃)₂·2CH₃OH}_n ( 2 ), and catena‐poly[[copper(II)‐bis{μ₂‐4‐amino‐3‐(pyridin‐2‐yl)‐5‐[(pyridin‐4‐ylmethyl)sulfanyl]‐1,2,4‐triazole}] bis(perchlorate) monohydrate], {[Cu(C₁₃H₁₂N₅S)₂](ClO₄)₂·H₂O}_n ( 3 ), were obtained from 4‐amino‐3‐(pyridin‐2‐yl)‐5‐[(pyridin‐3‐ylmethyl)sulfanyl]‐1,2,4‐triazole with pyridin‐3‐yl terminal groups and from 4‐amino‐3‐(pyridin‐2‐yl)‐5‐[(pyridin‐4‐ylmethyl)sulfanyl]‐1,2,4‐triazole with pyridin‐4‐yl terminal groups. Compound 1 displays a 2D net‐like structure. The 2D layers are further linked through hydrogen bonds between methanesulfonate anions and amino groups on the framework and guest H₂O molecules in the lattice to form a three‐dimensional (3D) structure. Compound 2 and 3 exhibit 1D chain structures, in which the complicated hydrogen‐bonding interactions play an important role in the formation of the 3D network. These experimental results indicate that the coordination orientation of the heteroatoms on the ligands has a great influence on the polymeric structures. Moreover, the selection of different counter‐anions, together with the inclusion of different guest solvent molecules, would also have a great effect on the hydrogen‐bonding systems in the crystal structures.     

A three‐dimensional coordination polymer of 3‐(3,5‐dicarboxybenzyloxy)benzoic acid with zinc

The synthesis is reported of the tricarboxylic acid 3‐(3,5‐dicarboxybenzyloxy)benzoic acid (H₃L) and the product of its reaction under solvothermal conditions with Zn^II cations, namely poly[[μ₆‐3‐(3,5‐dicarboxylatobenzyloxy)benzoato](dimethylformamide)‐μ₃‐hydroxido‐dizinc(II)], [Zn₂(C₁₆H₉O₇)(OH)(C₃H₇NO)]_n, the formation of which is associated with complete deprotonation of H₃L. Its crystal structure consists of a single‐framework coordination polymer of the organic L³⁻ ligand with Zn^II cations in a 1:2 ratio, with additional hydroxide and dimethylformamide (DMF) ligands coordinated to the Zn^II centres. The Zn^II cations are characterized by coordination numbers of 5 and 6, being bridged to each other by hydroxide ligands. In the polymeric framework, the carboxylate‐ and hydroxy‐bridged Zn^II cations are arranged in coordination‐tessellated columns, which propagate along the a axis of the crystal structure, and each L³⁻ ligand links to seven different Zn^II centres via Zn—O bonds of two different columns. The coordination framework, composed of [Zn₂(L)(OH)(DMF)]_n units, forms an open architecture, the channel voids within it being filled by the zinc‐coordinating DMF ligands. This report provides the first structural evidence for the formation of coordination polymers with H₃L via multiple metal–ligand bonds through its carboxylate groups.<!?tpb=21.5pt>     

A new one‐dimensional coordination polymer of 5‐(1,3‐dioxo‐4,5,6,7‐tetraphenylisoindolin‐2‐yl)isophthalic acid with manganese

The coordination polymer catena‐poly[[(dimethylformamide‐κO)[μ₃‐5‐(1,3‐dioxo‐4,5,6,7‐tetraphenylisoindolin‐2‐yl)isophthalato‐κ⁴O¹,O^1′:O³:O^3′](methanol‐κO)manganese(III)] dimethylformamide monosolvate], {[Mn(C₄₀H₂₃NO₆)(CH₃OH)(C₃H₇NO)]·C₃H₇NO}_n, has been synthesized from the reaction of 5‐(1,3‐dioxo‐4,5,6,7‐tetraphenylisoindolin‐2‐yl)isophthalic acid and manganese(II) acetate tetrahydrate in a glass tube at room temperature by solvent diffusion. The Mn^II centre is hexacoordinated by two O atoms from one chelating carboxylate group, by two O atoms from two monodentate carboxylate groups and by one O atom each from a methanol and a dimethylformamide (DMF) ligand. The single‐crystal structure crystallizes in the triclinic space group P. Moreover, the coordination polymer shows one‐dimensional 2‐connected {0} uninodal chain networks, and free DMF molecules are connected to the chains by O—H...O hydrogen bonds. The thermogravimetric and photoluminescent properties of the compound have also been investigated.     

A new two‐dimensional ZnII coordination polymer constructed by a multidentate N‐heterocyclic ligand and 5‐carboxybenzene‐1,3‐dicarboxylate

In the coordination polymer, poly[[{μ‐1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐imidazole‐κ²N:N′}(μ‐5‐carboxybenzene‐1,3‐dicarboxylato‐κ²O¹:O³)zinc(II)] dimethylformamide monosolvate pentahydrate], {[Zn(C₉H₄O₆)(C₁₁H₁₀N₄)]·C₃H₇NO·5H₂O}_n, the Zn^II ion is coordinated by two N atoms from two symmetry‐related 1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐imidazole (bmi) ligands and two O atoms from two symmetry‐related 5‐carboxybenzene‐1,3‐dicarboxylate (Hbtc²⁻) ligands in a slightly distorted tetrahedral geometry. The Zn^II ions are bridged by Hbtc²⁻ and bmi ligands, leading to a 4‐connected two‐dimensional network with the topological notation (4⁴.6²). Adjacent layers are further connected by 12 kinds of hydrogen bonds and also by π–π interactions, resulting in a three‐dimensional supramolecular architecture in the solid state.