Poly[[bis{μ2‐N2,N6‐bis[(pyridin‐3‐yl)methyl]pyridine‐2,6‐dicarboxamide}dichloridonickel(II)] N,N‐dimethylformamide tetrasolvate]

In the title compound, {[NiCl₂(C₁₉H₁₇N₅O₂)₂]·4C₃H₇NO}_n, the Ni^II atom is located on an inversion centre and is in a six‐coordinated octahedral geometry, formed by four pyridine N atoms from four N²,N⁶‐bis[(pyridin‐3‐yl)methyl]pyridine‐2,6‐dicarboxamide (BPDA) ligands occupying the equatorial plane and two chloride anions at the axial sites. The bidentate bridging BPDA ligands link the Ni^II atoms into a two‐dimensional corrugated grid‐like flexible layer with a (4,4)‐connected topology, which consists of left‐ and right‐handed helical chains sharing the common Ni^II atoms. Investigation of the thermal stability shows that the network is stable up to 573 K.     

catena‐Poly[[[diaqua[3‐(pyridin‐4‐yl)benzoato‐κ2O,O′]terbium(III)]‐bis[μ‐3‐(pyridin‐4‐yl)benzoato‐κ2O:O′]] monohydrate]

In the title compound, {[Tb(C₁₂H₈NO₂)₃(H₂O)₂]·H₂O}_n, the Tb^III cation is in an eight‐coordinate environment, ligated by six carboxylate O atoms from five 3‐(pyridin‐4‐yl)benzoate (L) ligands and by two O atoms from water molecules. The cations are bridged by the carboxylate O atoms of the L ligands to form a two‐stranded polymeric chain which is assembled into a three‐dimensional supramolecular network through regular interchain O—H...N hydrogen bonding. On excitation at 320 nm, the title compound displays a series of emissions, which were assigned to the characteristic electronic transitions of Tb^III.     

catena‐Poly[[[diaqua­bis(pyridine‐4‐carboxamide‐κN)copper(II)]‐μ2‐squarato‐κO1:O3] dihydrate]

The asymmetric unit of the title compound, {[Cu(C₄O₄)(C₆H₆N₂O)₂(H₂O)₂]·2H₂O}_n, consists of one pyridine‐4‐carbox­amide (isonicotinamide or ina) ligand, one‐half of a squarate dianion, a coordinated aqua ligand and a solvent water mol­ecule. Both the Cu^II and the squarate ions are located on inversion centers. The Cu^II ions are octa­hedrally surrounded by four O atoms of two water mol­ecules and two squarate anions, and by two N atoms of the isonicotinamide ligands. The crystal structure contains chains of squarate‐1,3‐bridged Cu^II ions. These chains are held together by N—H⋯O and O—H⋯O inter­molecular hydrogen‐bond inter­actions, forming an extensive three‐dimensional network.     

Poly[[μ2‐1,3‐bis(pyridin‐4‐yl)propane](μ3‐1,4‐phenylenediacetato)cadmium]

Solvothermal reaction between Cd(NO₃)₂, 1,4‐phenylenediacetate (1,4‐PDA) and 1,3‐bis(pyridin‐4‐yl)propane (bpp) afforded the title complex, [Cd(C₁₀H₈O₄)(C₁₃H₁₄N₂)]_n. Adjacent carboxylate‐bridged Cd^II ions are related by an inversion centre. The 1,4‐PDA ligands adopt a cis conformation and connect the Cd^II ions to form a one‐dimensional chain extending along the c axis. These chains are in turn linked into a two‐dimensional network through bpp bridges. The bpp ligands adopt an anti–gauche conformation. From a topological point of view, each bpp ligand and each pair of 1,4‐PDA ligands can be considered as linkers, while the dinuclear Cd^II unit can be regarded as a 6‐connecting node. Thus, the structure can be simplified to a two‐dimensional 6‐connected network.     

catena‐Poly[[[2,4‐dichloro‐6‐(pyridin‐2‐ylmethyl­iminomethyl)phenolato]copper(II)]‐μ‐thio­cyanato]

The title complex, [Cu(C₁₃H₉Cl₂N₂O)(NCS)]_n, is a novel thio­cyanate‐bridged polynuclear copper(II) compound. The Cu^II atom is five‐coordinated in a square‐pyramidal configuration, with one O and two N atoms of one Schiff base ligand and one terminal N atom of a bridging thio­cyanate ligand defining the basal plane, and one terminal S atom of another bridging thio­cyanate ligand occupying the axial position. The [2,4‐dichloro‐6‐(pyridin‐2‐ylmethyl­imino­methyl)­phenolato]­copper(II) moieties are linked by the bridging thio­cyanate ligands, forming polymeric chains running along the a axis.     

Hexaaquacobalt(II) and hexaaquanickel(II) bis(μ‐pyridine‐2,6‐dicarboxylato)bis[(pyridine‐2,6‐dicarboxylato)bismuthate(III)] dihydrate

The title complexes, hexaaquacobalt(II) bis(μ‐pyridine‐2,6‐dicarboxylato)bis[(pyridine‐2,6‐dicarboxylato)bismuthate(III)] dihydrate, [Co(H₂O)₆][Bi₂(C₇H₄NO₄)₄]·2H₂O, (I), and hexaaquanickel(II) bis(μ‐pyridine‐2,6‐dicarboxylato)bis[(pyridine‐2,6‐dicarboxylato)bismuthate(III)] dihydrate, [Ni(H₂O)₆][Bi₂(C₇H₄NO₄)₄]·2H₂O, (II), are isomorphous and crystallize in the triclinic space group P. The transition metal ions are located on the inversion centre and adopt slightly distorted MO₆ (M = Co or Ni) octahedral geometries. Two [Bi(pydc)₂]⁻ units (pydc is pyridine‐2,6‐dicarboxylate) are linked via bridging carboxylate groups into centrosymmetric [Bi₂(pydc)₄]²⁻ dianions. The crystal packing reveals that the [M(H₂O)₆]²⁺ cations, [Bi₂(pydc)₄]²⁻ anions and solvent water molecules form multiple hydrogen bonds to generate a supramolecular three‐dimensional network. The formation of secondary Bi...O bonds between adjacent [Bi₂(pydc)₄]²⁻ dimers provides an additional supramolecular synthon that directs and facilitates the crystal packing of both (I) and (II).     

Poly[bis{μ2‐4‐[3,5‐bis(pyridin‐4‐yl)phenyl]pyridine}nona‐μ2‐oxido‐tetraoxidocopper(II)tetramolybdenum(VI)]

The title compound, [CuMo₄O₁₃(C₂₁H₁₅N₃)₂]_n, was synthesized by the reaction of ammonium molybdate, copper acetate and 4‐[3,5‐bis(pyridin‐4‐yl)phenyl]pyridine (DPPP) in an aqueous medium under hydrothermal conditions. The two unique molybdenum centers and the copper center adopt MoO₄ tetrahedral, MoO₅N octahedral and CuO₄N₂ octahedral geometries, respectively. These polyhedra are connected to each other through corner‐sharing to form a two‐dimensional Cu–Mo–O layer, which is further linked by the DPPP ligands to form the three‐dimensional inorganic–organic hybrid framework.     

catena‐Poly[[di‐μ‐chloro‐bis[(triphenylphosphine)silver(I)]]‐μ‐2‐aminopyrimidine‐κ2N1:N3]

In the title supramolecular complex, [Ag₂Cl₂(C₄H₅N₃)(C₁₈H₁₅P)₂]_n, a one‐dimensional chain is formed by dimeric {Ag₂Cl₂(PPh₃)₂} units bridged by 2‐amino­pyrimidine moieties. The Ag atoms are four‐coordinate, with an AgCl₂NP core. A crystallographic inversion centre is located in the centre of the Ag₂Cl₂ chelate ring, while the crystallographic twofold axis bisects the 2‐amino­pyrimidine ligand.     

catena‐Poly[[bis(μ‐2‐sulfonatobenzoato)bis[triaquagadolinium(III)]]‐μ‐oxalato]

The asymmetric unit of the title coordination polymer, [Gd₂(C₇H₄O₅S)₂(C₂O₄)(H₂O)₆]_n or [Gd(2‐SB)(ox)_0.5(H₂O)₃]_2n (2‐SB is 2‐sulfonatobenzoate and ox is oxalate), (I), consists of one Gd^III ion, one 2‐SB anion, three coordinated water molecules and one half of an ox ligand. The ox ligand is located on a crystallographic inversion centre. The Gd^III centre shows a distorted tricapped trigonal–prismatic coordination formed by nine O atoms from two 2‐SB anions, one ox ligand and three coordinated water molecules. The carboxylate and sulfonate groups of the 2‐SB anions adopt μ₂‐η¹:η² and μ₁‐η⁰:η⁰:η¹ coordination modes to link two Gd^III ions, generating a centrosymmetric binuclear [Gd₂(2‐SB)₂(H₂O)₆]²⁻ subunit. The ox ligand acts as a bridge, linking the binuclear [Gd₂(2‐SB)₂(H₂O)₆]²⁻ subunits into a one‐dimensional chain structure parallel to the b axis. Furthermore, extensive O—H...O hydrogen bonds connect the chains into a three‐dimensional supramolecular architecture.     

Poly[bis[μ2‐3‐(pyridin‐4‐yl)benzoato‐κ3N:O,O′]lead(II)]

In the title compound, [Pb(C₁₂H₈NO₂)₂]_n, 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 (L) ligands and by two N atoms from another two ligands. Each ligand bridges two Pb^II centres, extending the structure into a corrugated two‐dimensional (4,4) net. The ligand L is conformationally chiral, with a torsion angle of 27.9 (12)° between the planes of its two rings. The torsion angle has the same sense throughout the structure, so that the extended two‐dimensional polymer is homochiral. Investigation of the thermal stability shows that the network is stable up to 613 K. In the absence of any stereoselective factor in the preparation of the compound, the enantiomeric purity of the crystal studied, based only on the torsional conformation of the ligand, implies that the bulk sample is a racemic conglomerate.     

catena‐Poly[bis{μ‐dihydrogen [(5‐carboxypentylimino)dimethylene]diphosphonato‐κ2O:O′}cadmium(II)]

The title compound, [Cd(C₈H₁₈NO₈P₂)₂]_n, synthesized by hydrothermal methods, exhibits a layered structure in which the Cd^II ion, occupying a centre of symmetry, is coordinated by six O atoms from four phosphonate ligands. The crosslinkage of CdO₆ octahedra by bridging phosphonate ligands results in a cadmium(II) phosphonate layer. Within the layer, there exists a 16‐membered ring incorporating four –Cd—O—P—O– linkages. The uncoordinated carboxyl group of the ligand is oriented so that it penetrates the adjacent layer, taking part in hydrogen bonding to two uncoordinated phosphonate O atoms to form a CO₂H/HO₂P motif.     

Bis[μ‐N,N′‐bis(quinolin‐8‐yl)pyridine‐2,6‐dicarboxamido]dizinc(II) dichloromethane disolvate

The title compound, [Zn₂(C₂₅H₁₅N₅O₂)₂]·2CH₂Cl₂, is a dinuclear double‐helical complex which lies on a crystallographic twofold axis. In the complex, both ligands are partitioned into two tridentate domains which allow each ligand to bridge both metal centres. Each Zn^II atom is six‐coordinated in a distorted octahedral environment formed by two amide N atoms, two quinoline N atoms and two pyridine N atoms from two different ligand molecules, with the central pyridine ring, unusually, bridging two Zn^II atoms. The deprotonated ligand is not planar, the amide side chains being considerably twisted out from the plane of the central pyridine ring.     

catena‐Poly[[dinitratocadmium(II)]bis[μ‐bis(2‐methyl‐1H‐imidazol‐1‐yl)methane‐κ2N3:N3′]]

The title compound, [Cd(NO₃)₂(C₉H₁₂N₄)₂]_n, has a one‐dimensional double‐bridged chain polymer structure with a 16‐membered macrometallacyclic tetragonal structural motif. The Cd^II ion occupies a crystallographic inversion centre and is coordinated by four equatorial N atoms from four distinct bis(2‐methylimidazol‐1‐yl)methane ligands and two apical nitrate O atoms to form a slightly distorted octahedral coordination geometry.     

Two nickel(II) bis[(pyridin‐2‐yl)methyl]amine complexes with homophthalic and benzene‐1,2,4,5‐tetracarboxylic acids

Two new Ni^II complexes involving the ancillary ligand bis[(pyridin‐2‐yl)methyl]amine (bpma) and two different carboxylate ligands, i.e. homophthalate [hph; systematic name: 2‐(2‐carboxylatophenyl)acetate] and benzene‐1,2,4,5‐tetracarboxylate (btc), namely catena‐poly[[aqua{bis[(pyridin‐2‐yl)methyl]amine‐κ³N,N′,N′′}nickel(II)]‐μ‐2‐(2‐carboxylatophenyl)aceteto‐κ²O:O′], [Ni(C₉H₆O₄)(C₁₂H₁₃N₃)(H₂O)]_n, and (μ‐benzene‐1,2,4,5‐tetracarboxylato‐κ⁴O¹,O²:O⁴,O⁵)bis(aqua{bis[(pyridin‐2‐yl)methyl]amine‐κ³N,N′,N′′}nickel(II)) bis(triaqua{bis[(pyridin‐2‐yl)methyl]amine‐κ³N,N′,N′′}nickel(II)) benzene‐1,2,4,5‐tetracarboxylate hexahydrate, [Ni₂(C₁₀H₂O₈)(C₁₂H₁₃N₃)₂(H₂O)₂]·[Ni(C₁₂H₁₃N₃)(H₂O)₃]₂(C₁₀H₂O₈)·6H₂O, (II), are presented. Compound (I) is a one‐dimensional polymer with hph acting as a bridging ligand and with the chains linked by weak C—H...O interactions. The structure of compound (II) is much more complex, with two independent Ni^II centres having different environments, one of them as part of centrosymmetric [Ni(bpma)(H₂O)]₂(btc) dinuclear complexes and the other in mononuclear [Ni(bpma)(H₂O)₃]²⁺ cations which (in a 2:1 ratio) provide charge balance for btc⁴⁻ anions. A profuse hydrogen‐bonding scheme, where both coordinated and crystal water molecules play a crucial role, provides the supramolecular linkage of the different groups.     

catena‐Poly[[[N,N′‐bis­(salicyl­idene)propane‐1,3‐diaminato]cobalt(III)]‐μ‐azido] and catena‐poly[[[N,N′‐bis(salicyl­idene)propane‐1,3‐diaminato]cobalt(III)]‐μ‐thio­cyanato]

The two title complexes, catena‐poly[[{2,2′‐[1,3‐propane­diylbis(nitrilo­methyl­idyne)]diphenolato}cobalt(III)]‐μ‐azido], [Co(C₁₇H₁₆N₂O₂)(N₃)]_n, (I), and catena‐poly[[{2,2′‐[1,3‐propane­diylbis(nitrilo­methyl­idyne)]diphenolato}cobalt(III)]‐μ‐thio­cyanato], [Co(C₁₇H₁₆N₂O₂)(NCS)]_n, (II), are isomorphous polynuclear cobalt(III) compounds. In both structures, the Co^III atom is six‐coordinated in an octa­hedral configuration by two N atoms and two O atoms of one Schiff base, and two terminal N or S atoms from two bridging ligands. The [N,N′‐bis­(salicyl­idene)propane‐1,3‐diaminato]cobalt(III) moieties are linked by the bridging ligands, viz. azide in (I) and thio­cyanate in (II), giving zigzag polymeric chains with backbones of the type [–Co—N—N—N—Co]_n in (I) or [–Co—N—C—S—Co]_n in (II) running along the c axis.     

catena‐Poly[[bis[pentaaquaerbium(III)]‐μ‐benzenehexacarboxylato] tetrahydrate]

The title compound is composed of one‐dimensional polymeric {[Er₂(C₁₂O₁₂)(H₂O)₁₀]·4H₂O}_n chains containing Er in a slightly distorted antiprismatic eightfold coordination. The benzene­hexa­carboxyl­ate ion is located about an inversion centre. Water mol­ecules of crystallization, linked by hydrogen bonding to water mol­ecules of the rare earth coordination spheres or the carboxyl­ate groups of the organic ligands, fill the space generated by the packing of the separated chains.     

A fourfold interpenetrating diamondoid three‐dimensional coordination polymer: poly[[[μ2‐1,2‐bis(pyridin‐4‐yl)ethene‐κ2N:N′](μ2‐5‐hydroxyisophthalato‐κ2O1:O3)zinc(II)] 1,2‐bis(pyridin‐4‐yl)ethene hemisolvate]

In the title compound, {[Zn(C₈H₄O₅)(C₁₂H₁₀N₂)]·0.5C₁₂H₁₀N₂}_n or {[Zn(HO‐BDC)(bpe)]·0.5bpe}_n [HO‐H₂BDC is 5‐hydroxyisophthalic acid and bpe is 1,2‐bis(pyridin‐4‐yl)ethene], the asymmetric unit contains a Zn^II atom, one HO‐BDC ligand, one coordinated bpe ligand and half a noncoordinating bpe molecule with crystallographic inversion symmetry. Each Zn^II centre is four‐coordinated by two O atoms from two distinct HO‐BDC ligands and two N atoms from two different bpe ligands in a ZnO₂N₂ coordination environment. The three‐dimensional topology of the title compound corresponds to a fourfold interpenetrating diamondoid coordination polymer network, with the uncoordinated bpe ligands located in the cavities, hydrogen bonded to the main network via the hydroxy group of the HO‐H₂BDC ligand.     

catena‐Poly[[bis(nicotinamide‐κN1)copper(I)]‐μ‐thiocyanato‐κ2N:S]

The Cu^I cations in the title compound, [Cu(NCS)(C₆H₆N₂O)₂]_n, are coordinated by N atoms from each of two mirror‐related nicotin­amide ligands, as well as by one N atom of one thio­cyanate ligand and one S atom of a symmetry‐related thio­cyanate ligand, within a slightly distorted tetrahedron. The Cu^I cations and the thio­cyanate anions are located on a crystallographic mirror plane and the nicotin­amide ligands occupy general positions. The Cu^I cations are connected by the thio­cyanate anions to form chains in the direction of the crystallographic a axis. These chains are connected by hydrogen bonds between the amide H atoms and the O atoms of adjacent nicotin­amide ligands, to give a three‐dimensional structure.     

Poly[[bis(pyridin‐3‐ol)manganese(II)]‐di‐μ‐pyridin‐3‐olato]

In the title complex, [Mn(C₅H₄NO)₂(C₅H₅NO)₂]_n or [Mn(μ‐3‐PyO)₂(3‐PyOH)₂]_n (3‐PyO⁻ is the pyridin‐3‐olate anion and 3‐PyOH is pyridin‐3‐ol), the Mn^II atom lies on an inversion centre and has octahedral geometry, defined by two N atoms and two deprotonated exocyclic O atoms of symmetry‐related pyridin‐3‐olate ligands [Mn—N = 2.3559 (14) Å and Mn—O = 2.1703 (11) Å], as well as two N atoms of terminal 3‐PyOH ligands [Mn—N = 2.3482 (13) Å]. The Mn^II atoms are bridged by the deprotonated pyridin‐3‐olate anion into a layer structure, generating sheets in the (01) plane. These sheets are linked by O—H⋯O hydrogen bonds. There are also π–π and C—H⋯π interactions in the crystal structure.