A new two‐dimensional manganese(II) coordination polymer based on thiophene‐3,4‐dicarboxylic acid

A novel manganese coordination polymer, poly[(μ₅‐thiophene‐3,4‐dicarboxylato)manganese(II)], [Mn(C₆H₂O₄S)]_n, was synthesized hydrothermally using 3,4‐thiophenedicarboxylate (3,4‐tdc²⁻) as the organic linker. The asymmetric unit of the complex contains an Mn²⁺ cation and one half of a deprotonated 3,4‐tdc²⁻ anion, both residing on a twofold axis. Each Mn²⁺ centre is six‐coordinated by O atoms of bridging/chelating carboxylate groups from five 3,4‐tdc²⁻ anions, forming a slightly distorted octahedron. The Mn²⁺ centres are bridged by 3,4‐tdc²⁻ anions to give an infinite two‐dimensional layer which incorporates one‐dimensional Mn–O gridlike chains, and in which the 3,4‐tdc²⁻ anion adopts a novel hexadentate chelating and μ₅‐bridging coordination mode. The fully deprotonated 3,4‐tdc²⁻ anion exhibits unexpected efficiency as a ligand towards the Mn²⁺ centres, which it coordinates through all of its carboxylate O atoms to provide the novel coordination mode. The IR spectrum of the complex is also reported.     

A novel two‐dimensional nickel(II) coordination polymer with 1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene and azide ligands

The coordination geometry of the Ni^II atom in the title complex, poly[diazidobis[μ‐1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene‐κ²N⁴:N^4′]nickel(II)], [Ni(N₃)₂(C₁₂H₁₂N₆)₂]_n, is a distorted octahedron, in which the Ni^II atom lies on an inversion centre and is coordinated by four N atoms from the triazole rings of two symmetry‐related pairs of 1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene (bbtz) ligands and two N atoms from two symmetry‐related monodentate azide ligands. The Ni^II atoms are bridged by four bbtz ligands to form a two‐dimensional (4,4)‐network.     

A novel two‐dimensional cobalt(II) coordination polymer with 1,4‐bis(1,2,4‐triazol‐1‐yl­methyl)­benzene

In the crystal structure of the title complex, poly­[[di­azidocobalt(II)]‐di‐μ‐1,4‐bis(1,2,4‐triazol‐1‐yl­methyl)­benzene‐κ⁴N⁴:N^4′], [Co(N₃)₂(bbtz)₂]_n, where bbtz is 1,4‐bis(1,2,4‐triazol‐1‐yl­methyl)­benzene (C₁₂H₁₂N₆), the Co^II atom, which lies on an inversion centre, is six‐coordinated by four N atoms from four bbtz ligands and by two N atoms from two azide ligands, in a distorted octahedral coordination environment. The Co^II atoms are bridged by four bbtz ligands to form a two‐dimensional [4,4]‐network.     

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 twofold interpenetrating two‐dimensional zinc(II) coordination polymer: synthesis,crystal structure and physical properties

A novel twofold interpenetrating two‐dimensional (2D) Zn^II coordination framework, poly[[(μ‐1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene‐κ²N³:N³)(μ‐naphthalene‐2,6‐dicarboxylato‐κ²O²:O⁶)zinc(II)] dimethylformamide monosolvate], {[Zn(C₁₂H₆O₄)(C₁₄H₁₄N₄)]·C₃H₇NO}_n or {[Zn(1,3‐BMIB)(NDC)]·DMF}_n (I), where H₂NDC is naphthalene‐2,6‐dicarboxylic acid, 1,3‐BMIB is 1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene and DMF is dimethylformamide, was prepared and characterized through IR spectroscopy, elemental analysis, thermal analysis and single‐crystal X‐ray diffraction. Single‐crystal X‐ray diffraction analysis revealed that (I) exhibits an unusual twofold interpenetrating 2D network. In addition, it displays strong fluorescence emissions and a high photocatalytic activity for the degradation of Rhodamine B (RhB) under UV‐light irradiation.     

(4,4′‐Bipyridine)dichloroman­ganese(II), a two‐dimensional ­coordination polymer

The title compound, [MnCl₂(C₁₀H₈N₂)]_n, crystallizes with a two‐dimensional network constructed from linear chains of edge‐sharing MnCl₄ square‐planar units cross‐linked by bidentate 4,4′‐bi­pyridine bridges. The Mn atom and the bipyridine moieties lie on sites with 222 crystallographic symmetry; the Cl atom lies on a twofold axis. The bi­pyridine mol­ecule is twisted about the central C—C bond by 33.5 (3)°.     

A new two‐dimensional anionic cadmium(II) polymer constructed through thiocyanate coordination bridges

A new cadmium–thiocyanate complex, poly[4‐(dimethylamino)pyridin‐1‐ium [di‐μ‐thiocyanato‐κ²N:S;κ²S:N‐thiocyanato‐κN‐cadmium(II)]], {(C₇H₁₁N₂)[Cd(NCS)₃]}_n, was synthesized by the reaction of cadmium thiocyanate and 4‐(dimethylamino)pyridine hydrochloride in aqueous solution. In the crystal structure, each Cd^II ion is square‐pyramidally coordinated by three N and two S atoms from five different thiocyanate ligands, four of which are bridging. The thiocyanate ligands play different roles in the build up of the structure; one role results in the formation of [Cd₂(NCS)₂] building blocks, while the other links the building blocks and cations via N—H...S hydrogen bonds. The N—H...S hydrogen bonds and weak π–π stacking interactions are involved in the formation of both a two‐dimensional network structure and the supramolecular network.     

A two‐dimensional copper(II) coordination polymer based on 2‐propyl‐1H‐imidazole‐4,5‐dicarboxylic acid

Single‐crystal X‐ray diffraction analysis of poly[bis(μ₂‐5‐carboxy‐2‐propyl‐1H‐imidazole‐4‐carboxylato‐κ³N³,O⁴:O⁵)copper(II)], [Cu(C₈H₉N₂O₄)₂)]_n, indicates that one carboxylic acid group of the 2‐propyl‐1H‐imidazole‐4,5‐dicarboxylic acid (H₃PDI) ligand is deprotonated. The resulting H₂PDI⁻ anion, acting as a bridge, connects the Cu^II cations to form a two‐dimensional (4,4)‐connected layer. Adjacent layers are further linked through interlayer hydrogen‐bond interactions, resulting in a three‐dimensional supramolecular structure.     

A novel two‐dimensional MnII coordination polymer with 1,2‐bis­(imidazol‐1‐yl)­ethane

In the crystal structure of the title complex, poly­[[di­azido­manganese(II)]‐di‐μ‐1,2‐bis­(imidazol‐1‐yl)­ethane‐κ⁴N³:N^3′], [Mn(N₃)₂(C₈H₁₀N₄)₂]_n or [Mn(N₃)₂(bim)₂]_n, where bim is 1,2‐­bis(imidazol‐1‐yl)­ethane, each Mn^II atom is six‐coordinated in a distorted octahedral coordination environment to four N atoms from four bim ligands and two N atoms from two azide ligands. The Mn^II atoms, which lie on inversion centres, are bridged by four bim ligands to form a two‐dimensional (4,4)‐network. The azide ligands are monodentate (terminal).     

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.     

A two‐dimensional coordination polymer containing a two‐dimensional zinc–carboxylate layer constructed from helical chains: poly[(μ4‐benzene‐1,2‐dicarboxylato)zinc(II)]

The title compound, [Zn(C₈H₄O₄)]_n, consists of one Zn^II cation and one benzene‐1,2‐dicarboxylate dianion (BDC²⁻) as the building unit. The Zn^II cation is four‐coordinated by four carboxylate O atoms from four dianionic BDC²⁻ ligands in a distorted tetrahedral geometry. The Zn^II cations are linked by the BDC²⁻ ligands to generate a structure featuring two‐dimensional zinc–carboxylate layers containing left‐ and right‐handed helical chains. The two‐dimensional layers are stacked along the a direction. The thermal stability of the title compound has been studied.     

A novel one‐dimensional zinc coordination polymer containing 4‐methylbenzoate and 4,4‐bipyridine

The title compound, catena‐poly[[tris(μ‐4‐methylbenzoato)‐κ²O:O;κ⁴O:O′‐(4‐methylbenzoato‐κ²O,O′)dizinc(II)]‐μ‐4,4′‐bipyridine‐κ²N:N′], [Zn₂(C₈H₇O₂)₄(C₁₀H₈N₂)]_n, is a novel coordination polymer. The asymmetric unit contains two unique Zn^II ions, four 4‐methylbenzoate ligands and one 4,4′‐bipyridine (4,4′‐bpy) ligand, all in general positions. The four 4‐methylbenzoate ligands link the two Zn^II centres to form a dinuclear unit, with a Zn...Zn separation of 3.188 (2) Å, which can be regarded as a supramolecular secondary building unit (SBU). These SBUs are further bridged by 4,4′‐bpy ligands, forming a novel one‐dimensional infinite chain. There are π–π stacking interactions between the benzene rings of the 4‐methylbenzoate ligands and the pyridyl rings of the 4,4′‐bpy ligands, leading to the formation of a corrugated layer. These layers are further assembled via C—H...O hydrogen bonds into a three‐dimensional supramolecular network structure. Coordination polymers such as the title compound are of interest for their potential applications as functional materials.     

A two‐dimensional zinc(II) coordination polymer created via in situ ligand synthesis involving C—N bond formation

The novel Zn^II coordination polymer poly[{μ₄‐2‐[3‐(pyridin‐2‐yl)‐1H‐pyrazol‐3‐yl]butanedioato}zinc(II)], [Zn(C₁₂H₉N₃O₄)]_n, has been synthesized hydrothermally and structurally characterized. The results demonstrate that the complex shows two‐dimensional neutral wave‐like layers. The complex was prepared by the conjugate addition reaction of 2‐(1H‐pyrazol‐3‐yl)pyridine to cis‐fumaric acid in the presence of Zn(OAc)₂·2H₂O (OAc is acetate) at 413 K.     

A threefold interpenetrating two‐dimensional zinc(II) coordination polymer: synthesis,crystal structure and selective luminescence sensing properties

The Fe³⁺ ion is the most important element in environmental systems and plays a fundamental role in biological processes. Iron deficiency can result in diseases and highly selective and sensitive detection of trace Fe³⁺ has become a hot topic. A novel two‐dimensional Zn^II coordination framework, poly[[μ‐4,4′‐bis(2‐methylimidazol‐1‐yl)diphenyl ether‐κ²N³:N^3′](μ‐4,4′‐sulfonyldibenzoato‐κ²O:O′)zinc(II)], [Zn(C₁₄H₈O₆S)(C₂₀H₁₈N₄O)]_n or [Zn(SDBA)(BMIOPE)]_n, (I), where H₂SDBA is 4,4′‐sulfonyldibenzoic acid and BMIOPE is 4,4′‐bis(2‐methylimidazol‐1‐yl)diphenyl ether, has been prepared and characterized by IR, elemental analysis, thermal analysis and X‐ray diffraction analysis, the latter showing that the coordination polymer exhibits a threefold interpenetrating two‐dimensional 4⁴‐ sql network. In addition, it displays a highly selective and sensitive sensing for Fe³⁺ ions in aqueous solution.     

A novel two‐dimensional layered framework built of strontium(II) with 4‐nitrobenzene‐1,3‐dicarboxylic acid

In poly[[aquastrontium(II)]‐μ₆‐4‐nitrobenzene‐1,3‐dicarboxylato‐κ⁷O¹:O²:O²:O³:O³,O⁴:O⁴], [Sr(C₈H₃NO₆)(H₂O)]_n, the Sr^II ion displays a distorted bicapped triangular prismatic configuration, defined by seven carboxyl O atoms from six symmetry‐related ligands and one water molecule. The ligand molecules connect the Sr^II ions into a two‐dimensional layered framework in the ac plane, with close O...O contacts between the nitro groups and with each nitro group providing one acceptor O atom for a weak intermolecular C—H...O hydrogen bond.     

A novel two‐dimensional network cadmium(II) coordination polymer containing one 1,4‐bis­(1,2,4‐triazol‐1‐yl)butane and double dicyanamide bridges

In the crystal structure of the title complex, poly[μ‐1,4‐bis­(1,2,4‐triazol‐1‐yl)butane‐di‐μ‐1,5‐dicyanamido‐cadmium(II)], [Cd(C₂N₃)₂(C₈H₁₂N₆)]_n or [Cd(dca)₂(btb)]_n, where dca is dicyanamide and btb is 1,4‐bis­(1,2,4‐triazol‐1‐yl)butane, each Cd^II atom occupies a center of symmetry and is in a six‐coordinated distorted octa­hedral environment. Four N atoms from four dca ligands fill the equatorial positions, and two N atoms from two btb ligands occupy the axial positions. The dca ligands adopt an end‐to‐end coordination mode and link the Cd^II atoms to form a 12‐membered Cd(dca)₂Cd ring, and neighboring rings extend along the b axis to form a [Cd(dca)₂]_n chain. The btb ligands, acting as bridging bidentate ligands, link the Cd^II atoms of adjacent one‐dimensional [Cd(dca)₂]_n chains, forming a rhombic two‐dimensional network.     

A two‐dimensional cadmium(II) polymer based on nicotinic acid and thiocyanate ligands

A cadmium–thiocyanate complex, poly[[bis(nicotinic acid‐κN)di‐μ‐thiocyanato‐κ²N:S;κ²S:N‐cadmium(II)] monohydrate], {[Cd(NCS)₂(C₆H₅NO₂)₂]·H₂O}_n, was synthesized by the reaction of nicotinic acid, cadmium nitrate tetrahydrate and potassium thiocyanide in aqueous solution. In the crystal structure, each Cd^II cation is in a distorted octahedral coordination environment, coordinated by the N and S atoms of nicotinic acid and thiocyanate ligands. Neighbouring Cd^II cations are linked together by thiocyanate bridges to form a two‐dimensional network. Hydrogen‐bond interactions between the uncoordinated solvent water molecules and the organic ligands result in the formation of the three‐dimensional supramolecular network.     

A novel two‐dimensional CdII coordination polymer: poly[aqua[μ4‐2‐(4‐carboxylatobenzoyl)benzoato]cadmium(II)]

The title Cd^II coordination framework, [Cd(C₁₅H₈O₅)(H₂O)]_n or [Cd(bpdc)(H₂O)]_n [H₂bpdc is 2‐(4‐carboxybenzoyl)benzoic acid], has been prepared and characterized using IR spectroscopy, elemental analysis, thermal analysis and single‐crystal X‐ray diffraction. Each Cd^II centre is six‐coordinated by two O atoms from one 2‐(4‐carboxylatobenzoyl)benzoate (bpdc²⁻) ligand in chelating mode, three O‐donor atoms from three other bpdc²⁻ anions and one O atom from a coordinated water molecule in an octahedral coordination environment. Two crystallographically equivalent Cd^II cations are bridged by one O atom of the 2‐carboxylate group of one bpdc²⁻ ligand and by both O atoms of the 4‐carboxylate group of a second bpdc²⁻ ligand to form a binuclear [(Cd)₂(O)(OCO)] secondary building unit. Adjacent secondary building units are interlinked to form a one‐dimensional [Cd(OCO)₂]_n chain. The bpdc²⁻ ligands link these rod‐shaped chains to give rise to a complex two‐dimensional [Cd(bpdc)]_n framework with a 4,4‐connected binodal net topology of point symbol {4³.6².8}. The compound exhibits a strong fluorescence emission and typical ferroelectric behaviour in the solid state at room temperature.     

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

In poly[[μ₃‐2,2′‐(disulfanediyl)dibenzoato‐κ⁵O:O,O′:O′′,O′′′](1,10‐phenanthroline‐κ²N,N′)cadmium(II)], [Cd(C₁₄H₈O₄S₂)(C₁₂H₈N₂)]_n, the asymmetric unit contains one Cd^II cation, one 2,2′‐(disulfanediyl)dibenzoate anion (denoted dtdb²⁻) and one 1,10‐phenanthroline ligand (denoted phen). Each Cd^II 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 Cd^II 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.     

A novel nickel(II) coordination polymer incorporating 1,4‐phenylene­diacetic acid and 1,10‐phenanthroline

The title nickel(II) coordination polymer, viz. poly[[bis­(1,10‐phenanthroline)tris­(μ₃‐1,4‐phenyl­enediacetato)trinickel(II)] dihydrate], {[Ni₃(C₁₀H₈O₄)₃(C₁₂H₈N₂)₂]·2H₂O}_n, consists of linear trinuclear building blocks with two crystallographically unique Ni atoms. One Ni^II atom and the geometric centre of one 1,4‐phenyl­enediacetate ligand in the trinuclear unit both lie on inversion centres, while the other unique Ni^II atom lies near the inversion centre, together with another 1,4‐phenyl­enediacetate ligand. Each pair of adjacent trinuclear units is bridged by 1,4‐phenyl­enediacetate ligands, forming two kinds of infinite chains along the a and b axes, respectively. These two kinds of chains crosslink to yield a two‐dimensional network in the ab plane. The two‐dimensional sheets further stack along the c axis viaπ–π stacking inter­actions and hydrogen bonds, forming a three‐dimensional supramolecular structure.