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 three‐dimensional copper(II) coordination polymer with 1,4‐bis(1,2,4‐triazol‐1‐ylmeth­yl)benzene and thio­cyanate

In the title complex, poly[copper(II)‐di‐μ₂‐thio­cyanato‐μ₂‐1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene], [Cu(NCS)₂(C₁₂H₁₂N₆)]_n, the Cu^II atom lies on an inversion centre in a tetra­gonally distorted octa­hedral environment. Four N atoms from thio­cyanate and 1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene (bbtz) ligands fill the equatorial positions, and S atoms from symmetry‐related thio­cyanate ligands fill the axial positions. The benzene ring of the bbtz ligand lies about an inversion centre. Single thio­cyanate bridges link the Cu^II atoms into two‐dimensional sheets containing an unprecedented 16‐membered [Cu₄(μ‐NCS‐N:S)₄] ring. The bbtz ligands further link the two‐dimensional sheets into a three‐dimensional network.     

A novel three‐dimensional cadmium(II) coordination polymer incorporating 1,4‐bis­(1,2,4‐triazol‐1‐ylmethyl)­benzene and thio­cyanate

In the title complex, poly[cadmium(II)‐μ₂‐1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene‐di‐μ₂‐thio­cyanato], [Cd(NCS)₂(C₁₂H₁₂N₆)]_n, the Cd^II atom lies on an inversion centre in a distorted octa­hedral environment. Four N atoms from the thio­cyanate and 1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene (bbtz) ligands occupy the equatorial positions, and two S atoms from symmetry‐related thio­cyanate ligands occupy the axial positions. The benzene ring of the bbtz ligand lies about an inversion centre. Single thio­cyanate bridges link the Cd^II atoms into two‐dimensional sheets containing novel 16‐membered [Cd₄(μ‐NCS‐N:S)₄] rings. The bbtz ligands further link these two‐dimensional sheets into an unprecedented covalent three‐dimensional network for the cadmium–thio­cyanate system.     

Magnetic investigations of a two‐dimensional coordination polymer with a three‐dimensional supramolecular framework: poly[[bis[μ2‐1,4‐bis(1,2,4‐triazol‐1‐yl)butane]bis(thiocyanato‐κN)cobalt(II)] dihydrate]

In the title mixed‐ligand metal–organic polymeric complex, {[Co(NCS)₂(C₈H₁₂N₆)₂]·2H₂O}_n, the asymmetric unit contains a divalent Co^II cation, which sits on an inversion centre, two halves of two crystallographically distinct and centrosymmetric 1,4‐bis(1,2,4‐triazol‐1‐yl)butane (BTB) ligands, one N‐bound thiocyanate ligand and one solvent water molecule. The Co^II atom possesses a distorted {CoN₆} octahedral geometry, with the equatorial positions taken up by triazole N atoms from four different BTB ligands. The axial positions are filled by thiocyanate N atoms. In the crystal, each Co^II atom is linked covalently to four others through the distal donors of the tethering BTB ligands, forming a neutral (4,4)‐topology two‐dimensional rhomboid grid layer motif, which is coincident with the (11) crystal planes. Magnetic investigations show that weak antiferromagnetic coupling exists between Co^II atoms in the complex.     

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 three‐dimensional cadmium coordination polymer based on 1,4‐bis(1,2,4‐triazol‐1‐yl)but‐2‐ene and benzene‐1,3,5‐tricarboxylic acid

The Cd^II three‐dimensional coordination poly[[[μ₄‐1,4‐bis(1,2,4‐triazol‐1‐yl)but‐2‐ene]bis(μ₃‐5‐carboxybenzene‐1,3‐dicarboxylato)dicadmium(II)] dihydrate], {[Cd₂(C₉H₄O₆)₂(C₈H₁₀N₆)]·2H₂O}_n , (I), has been synthesized by the hydrothermal reaction of Cd(NO₃)₂·4H₂O, benzene‐1,3,5‐tricarboxylic acid (1,3,5‐H₃BTC) and 1,4‐bis(1,2,4‐triazol‐1‐yl)but‐2‐ene (1,4‐btbe). The IR spectrum suggests the presence of protonated carboxylic acid, deprotonated carboxylate and triazolyl groups. The purity of the bulk sample was confirmed by elemental analysis and X‐ray powder diffraction. Single‐crystal X‐ray diffraction analysis reveals that the Cd^II ions adopt a five‐coordinated distorted trigonal–bipyramidal geometry, coordinated by three O atoms from three different 1,3,5‐HBTC²⁻ ligands and two N atoms from two different 1,4‐btbe ligands; the latter are situated on centres of inversion. The Cd^II centres are bridged by 1,3,5‐HBTC²⁻ and 1,4‐btbe ligands into an overall three‐dimensional framework. When the Cd^II centres and the tetradentate 1,4‐btbe ligands are regarded as nodes, the three‐dimensional topology can be simplified as a binodal 4,6‐connected network. Thermogravimetric analysis confirms the presence of lattice water in (I). Photoluminescence studies imply that the emission of (I) may be ascribed to intraligand fluorescence.     

A novel dimeric zinc(II) complex: bis­[μ‐1,2‐bis­(1H‐1,2,4‐triazol‐1‐yl)­ethane‐κ2N4:N4′]­bis­[diisothio­cyanato­zinc(II)]

The coordination geometry of the Zn^II atom in the title complex, [Zn₂(NCS)₄(C₆H₈N₆)₂], is that of a distorted tetra­hedron, in which the Zn^II atom is coordinated by four N atoms from the triazole rings of two symmetry‐related 1,2‐bis­(1,2,4‐triazol‐1‐yl)ethane ligands and two thio­cyanate ligands. Two Zn^II atoms are bridged by two organic ligands to form a dimer. The dimer lies about an inversion center.     

catena‐Poly[[diisothio­cyanato­cad­mium(II)]‐bis­[μ‐1,3‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene‐κ2N4:N4′]]: a double‐chain coordination polymer

The coordination geometry of the Cd^II atom in the title complex, [Cd(NCS)₂(C₁₂H₁₂N₆)₂]_n or [Cd(NCS)₂(mbtz)₂]_n, where mbtz is 1,3‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene, is a distorted compressed octa­hedron in which the Cd^II atom lies on an inversion centre, coordinated by four N atoms from the triazole rings of four mbtz ligands and two N atoms from two monodentate NCS⁻ ligands. The structure is polymeric, with 24‐membered spiro‐fused rings extending along [100] and with the 24‐membered ring containing two inversion‐related mbtz mol­ecules.     

A novel parallel interpenetrating two‐dimensional (4,4) network: poly[[μ2‐1,4‐bis(imidazol‐1‐ylmethyl)benzene](μ2‐naphthalene‐1,4‐dicarboxylato)zinc(II)]

In the title coordination compound, [Zn(C₁₂H₆O₄)(C₁₄H₁₄N₄)]_n, the two Zn^II centers exhibit different coordination environments. One Zn^II center is four‐coordinated in a distorted tetrahedral environment surrounded by two carboxylate O atoms from two different naphthalene‐1,4‐dicarboxylate (1,4‐ndc) anions and two N atoms from two distinct 1,4‐bis(imidazol‐1‐ylmethyl)benzene (1,4‐bix) ligands. The coordination of the second Zn^II center comprises two N atoms from two different 1,4‐bix ligands and three carboxylate O atoms from two different 1,4‐ndc ligands in a highly distorted square‐pyramidal environment. The 1,4‐bix ligand and the 1,4‐ndc anion link adjacent Zn^II centers into a two‐dimensional four‐connected (4,4) network. The two (4,4) networks are interpenetrated in a parallel mode.     

The infinite double‐stranded chain polymer catena‐poly­[[bis­(dicyan­amido)­zinc(II)]‐di‐μ‐1,2‐bis(1,2,4‐triazol‐1‐yl)­ethane‐κ4N4:N4′]

The coordination geometry of the Zn^II atom in the title complex, [Zn(C₂N₃)₂(C₆H₈N₆)₂]_n or [Zn(dca)₂(bte)₂]_n, where bte is μ‐1,2‐bis(1,2,4‐triazol‐1‐yl)­ethane and dca is dicyan­amide, is distorted compressed octahedral, in which the Zn^II atom lies on an inversion center and coordinates four N atoms from the triazole rings of four symmetry‐related bte ligands and two N atoms from two symmetry‐related monodentate dca ligands. The structure is polymeric, with 18‐membered spiro‐fused rings extending in the b direction and each 18‐membered ring involving two inversion‐related bte mol­ecules.     

A fivefold interpenetrating diamond‐like three‐dimensional metal–organic framework: poly[(μ2‐benzene‐1,4‐diacetato)[μ2‐1,6‐bis(1,2,4‐triazol‐1‐yl)hexane]zinc(II)]

In the mixed‐ligand metal–organic title polymeric compound, [Zn(C₁₀H₈O₄)(C₁₀H₁₆N₆)]_n or [Zn(PBEA)(BTH)]_n [H₂PBEA is benzene‐1,4‐diacetic acid and BTH is 1,6‐bis(1,2,4‐triazol‐1‐yl)hexane], the asymmetric unit contains a Zn^II atom, one half of a BTH ligand and one half of a doubly deprotonated H₂PBEA ligand. Each Zn^II centre lies on a crystallographic twofold rotation axis and is four‐coordinated by two O atoms from two distinct PBEA²⁻ ligands and two N atoms from two different BTH ligands in a {ZnO₂N₂} coordination environment. The three‐dimensional topology of the title compound corresponds to that of a fivefold interpenetrating diamond‐like metal–organic framework.     

Poly­[[di­aqua­cobalt(II)]‐μ‐4,4′‐bi­pyridine‐κ2N:N′‐μ‐p‐phenyl­enebis­(oxy­acetato)‐κ2O:O′]

The title compound, [Co^II(C₁₀H₈O₆)(C₁₀H₈N₂)(H₂O)₂]_n, was obtained by the hydro­thermal reaction of CoSO₄ with benzene‐1,4‐dioxy­di­acetate [systematic name: p‐phenyl­ene­bis­(oxy­acetate)] and 4,4′‐bi­pyridine (4,4′‐bpy). The Co atom lies at an inversion center and the benzene‐1,4‐dioxydiacetate and 4,4′‐bipyridine moieties lie about other inversion centers. The benzene‐1,4‐dioxydiacetate ligands bridge the octahedral Co^II coordination centers, forming a one‐dimensional zigzag chain. The chains are further bridged by 4,4′‐bpy ligands, forming a novel two‐dimensional supramolecular architecture. Hydro­gen‐bonding interactions between the coordinated water mol­ecules and the carboxyl­ate O atoms lead to the formation of a three‐dimensional network structure.     

Bis(acesulfamato‐κ2O4,N)bis­(3‐methyl­pyridine)copper(II)

In the crystal structure of the title compound {systematic name: bis­[6‐methyl‐1,2,3‐oxa­thia­zin‐4(3H)‐one 2,2‐dioxide(1−)‐κ²N³,O⁴]bis­(3‐meth­yl­pyridine)copper(II)}, [Cu(C₄H₄NO₄S)₂(C₆H₇N)₂], the Cu^II centre resides on a centre of symmetry and has an octa­hedral geometry that is distorted both by the presence of four‐membered chelate rings and because of the Jahn–Teller effect. The equatorial plane is formed by the N atoms of two methyl­pyridine ligands and by the more basic O atoms of the acesulfamate ligands, while the weakly basic N atoms of these ligands are in elongated axial positions with a misdirected valence. The crystal is stabilized by two inter­molecular C—H⋯O inter­actions involving the methyl and CH groups, and the sulfonyl O atoms of the acesulfamate group.     

Poly[(μ4‐biphenyl‐3,3′,4,4′‐tetracarboxylato)bis[μ2‐1,4‐bis(imidazol‐1‐ylmethyl)benzene]dicobalt(II)]

The asymmetric unit of the title two‐dimensional coordination polymer, [Co₂(C₁₆H₆O₈)(C₁₄H₁₄N₄)₂]_n, contains one Co²⁺ ion, half of a biphenyl‐3,3′,4,4′‐tetracarboxylate (bptc) anion lying about an inversion centre and one 1,4‐bis(imidazol‐1‐ylmethyl)benzene (bix) ligand. The Co^II atom is coordinated by three carboxylate O atoms from two different bptc ligands and two N atoms from two bix ligands constructing a distorted square pyramid. Each Co²⁺ ion is interlinked by two bptc anions, while each bptc anion coordinates to four Co atoms as a hexadentate ligand so that four Co^II atoms and four bptc anions afford a larger 38‐membered ring. These inorganic rings are further extended into a two‐dimensional undulated network in the (10) plane. Two Co^II atoms in adjacent 38‐membered rings are joined together by pairs of bix ligands forming a 26‐membered [Co₂(bix)₂] ring that is penetrated by a bptc anion; these components share a common inversion centre.     

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).     

Bis(5‐aminotetrazole‐1‐acetato‐κO)tetraaquacobalt(II) and catena‐poly[[cadmium(II)]‐bis(μ‐5‐aminotetrazole‐1‐acetato‐κ3N4:O,O′)]

The Co^II atom in bis(5‐aminotetrazole‐1‐acetato)tetraaquacobalt(II), [Co(C₃H₄N₅O₂)₂(H₂O)₄], (I), is octahedrally coordinated by six O atoms from two 5‐aminotetrazole‐1‐acetate (atza) ligands and four water molecules. The molecule has a crystallographic centre of symmetry located at the Co^II atom. The molecules of (I) are interlinked by hydrogen‐bond interactions, forming a two‐dimensional supramolecular network structure in the ac plane. The Cd^II atom in catena‐poly[[cadmium(II)]‐bis(μ‐5‐aminotetrazole‐1‐acetato], [Cd(C₃H₄N₅O₂)₂]_n, (II), lies on a twofold axis and is coordinated by two N atoms and four O atoms from four atza ligands to form a distorted octahedral coordination environment. The Cd^II centres are connected through tridentate atza bridging ligands to form a two‐dimensional layered structure extending along the ab plane, which is further linked into a three‐dimensional structure through hydrogen‐bond interactions.     

The mononuclear cobalt(II) complex CoII(DMBDIZ)2(NCS)2, where DMBDIZ is 2,6‐di­methyl­benzo[1,2‐d:4,5‐d′]­di­imidazole

In the title mononuclear cobalt complex, bis(2,6‐di­methyl‐1H,7H‐benzo­[1,2‐d:4,5‐d′]­di­imidazole‐κN³)­bis­(thio­cyanato‐κN)cobalt(II), [Co^II(NCS)₂(DMBDIZ)₂] or [Co(NCS)₂(C₁₀H₁₀N₄)₂], the cobalt(II) ion is coordinated to four N atoms, from two thio­cyanate anions and two DMBDIZ ligands, in a distorted tetrahedral geometry. In the DMBDIZ ligand, the two imine N atoms are positioned cis with respect to one another. The crystal packing of the complex is dominated by both hydrogen bonding, involving two N—H?N and two N—H?S interactions, and aromatic π–π stacking.     

A novel bridged asymmetric binuclear manganese(II) complex with DTPB [DTPB is 1,1,4,7,7‐pentakis(1H‐benz­imidazol‐2‐yl­methyl)‐1,4,7‐tri­aza­heptane]

The crystal structure of the title compound, tetra­chloro­[μ‐1,1,4,7,7‐pentakis(1H‐benzimidazol‐2‐yl­methyl)‐1,4,7‐tri­azaheptane]­dimanganese(II) methanol pentasolvate tetrahydrate, [Mn₂Cl₄(C₄₄H₄₃N₁₃)]·5CH₄O·4H₂O, contains an ­asymmetric dinuclear Mn^II–DTPB [DTPB is 1,1,4,7,7‐pentakis(1H‐benzimidazol‐2‐yl­methyl)‐1,4,7‐tri­aza­heptane] complex with an intra‐ligand bridging group (–NCH₂CH₂N–), as well as several solvate mol­ecules (methanol and water). Both Mn^II cations have similar distorted octahedral coordination geometries. One Mn^II cation is coordinated by a Cl⁻ anion and five N atoms from the ligand, and the other is coordinated by three Cl⁻ anions and three N atoms of the same ligand. The Mn⋯Mn distance is 7.94 Å. A Cl⋯H—O⋯H—O⋯H—N hydrogen‐bond chain is also observed, connecting the two parts of the complex.     

Poly[bis(μ‐benzene‐1,4‐dicarboxylato)bis[μ‐6‐(4‐pyridyl)‐5H‐imidazolo[4,5‐f][1,10]phenanthroline]dilead(II)]: an interpenetrating α‐Po net

The asymmetric unit of the title compound, [Pb₂(C₈H₄O₄)₂(C₁₈H₁₁N₅)₂]_n, contains two Pb^II atoms, two benzene‐1,4‐dicarboxylate (1,4‐bdc) dianions and two 6‐(4‐pyridyl)‐5H‐imidazolo[4,5‐f][1,10]phenanthroline (L) ligands. Each Pb^II atom is eight‐coordinated by three N atoms from two different L ligands and five carboxylate O atoms from three different 1,4‐bdc dianions. The two 1,4‐bdc dianions (1,4‐bdc₁ and 1,4‐bdc₂) show different coordination modes. Each 1,4‐bdc₁ coordinates to two Pb^II atoms in a chelating bis‐bidentate mode. Each carboxylate group of the 1,4‐bdc₂ anion connects two Pb^II atoms in a chelating–bridging tridentate mode to form a dinuclear unit. Neighbouring dinuclear units are connected together by the aromatic backbone of the 1,4‐bdc dianions and the L ligands into a three‐dimensional six‐connected α‐polonium framework. The most striking feature is that two identical three‐dimensional single α‐polonium nets are interlocked with each other, thus leading directly to the formation of a twofold interpenetrated three‐dimensional α‐polonium architecture. The framework is held together in part by strong N—H...O hydrogen bonds between the imidazole NH groups of the L ligands and the carboxylate O atoms of 1,4‐bdc dianions within different α‐polonium nets.     

A new three‐dimensional zinc(II) coordination polymer involving 2‐[(1H‐1,2,4‐triazol‐1‐yl)methyl]‐1H‐benzimidazole and benzene‐1,4‐dicarboxylate ligands

Metal–organic frameworks (MOFs) based on multidentate N‐heterocyclic ligands involving imidazole, triazole, tetrazole, benzimidazole, benzotriazole or pyridine present intriguing molecular topologies and have potential applications in ion exchange, magnetism, gas sorption and storage, catalysis, optics and biomedicine. The 2‐[(1H‐1,2,4‐triazol‐1‐yl)methyl]‐1H‐benzimidazole (tmb) ligand has four potential N‐atom donors and can act in monodentate, chelating, bridging and tridentate coordination modes in the construction of complexes, and can also act as both a hydrogen‐bond donor and acceptor. In addition, the tmb ligand can adopt different coordination conformations, resulting in complexes with helical structures due to the presence of the flexible methylene spacer. A new three‐dimensional coordination polymer, poly[[bis(μ₂‐benzene‐1,4‐dicarboxylato)‐κ⁴O¹,O^1′:O⁴,O^4′;κ²O¹:O⁴‐bis{μ₂‐2‐[(1H‐1,2,4‐triazol‐1‐yl)methyl‐κN⁴]‐1H‐benzimidazole‐κN³}dizinc(II)] trihydrate], {[Zn(C₈H₄O₄)(C₁₀H₉N₅)]·1.5H₂O}_n, has been synthesized by the reaction of ZnCl₂ with tmb and benzene‐1,4‐dicarboxylic acid (H₂bdic) under solvothermal conditions. There are two crystallographically distinct bdic²⁻ ligands [bdic²⁻(A) and bdic²⁻(B)] in the structure which adopt different coordination modes. The Zn^II ions are bridged by tmb ligands, leading to one‐dimensional helical chains with different handedness, and adjacent helices are linked by bdic²⁻(A) ligands, forming a two‐dimensional network structure. The two‐dimensional layers are further connected by bdic²⁻(B) ligands, resulting in a three‐dimensional framework with the topological notation 6⁶. The IR spectra and thermogravimetric curves are consistent with the results of the X‐ray crystal structure analysis and the title polymer exhibits good fluorescence in the solid state at room temperature.