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.     

Poly[(μ2‐1,3‐di‐4‐pyridylpropane‐κ2N:N′)(μ3‐glutarato‐κ3O:O′:O′′)dizinc(II)]

The title compound, [Zn₂(C₅H₆O₄)₂(C₁₃H₁₄N₂)]_n or [Zn₂(glu)₂(bpp)]_n, is a novel zinc polymer based on mixed flexible glutarate (glu) and 1,3‐di‐4‐pyridylpropane (bpp) ligands. The Zn^II center has a distorted tetra­hedral geometry and the central atom of the bpp ligand is located at a special site with a C₂ axis passing through it. A layer is formed by Zn–glu bonding. Such layers are pillared by bpp ligands, forming a three‐dimensional framework with large channels. The inverted inter­penetration of two three‐dimensional frameworks completes the mol­ecular structure.     

catena‐Poly[[copper(II)‐μ‐2‐[bis­(2‐pyridylmeth­yl)amino]butyrato‐κ4N,N′,N′′,O:κO′] perchlorate]

The copper(II) ion in the syn–anti carboxyl­ate‐bridged one‐dimensional zigzag chain title complex, {[Cu(C₁₆H₁₈N₃O₂)]ClO₄}_n, exhibits a distorted trigonal–bipyramidal environment. Two N atoms and one carboxyl­ate O atom of the ligand form the basal plane, while the axial positions are filled by an N atom of the ligand and one O atom belonging to the carboxyl­ate group of an adjacent mol­ecule. The crystal packing is enhanced by C—H⋯O(perchlorate) hydrogen bonds.     

catena‐Poly[[diiodo­zinc(II)]‐μ‐4,4′‐bipyridine‐κ2N:N′]

The title compound, [ZnI₂(bipy)]_n (bipy is 4,4′‐bipyridine, C₁₀H₈N₂), has been prepared by the hydro­thermal reaction of ZnI₂ and bipy at 433 K. Each Zn atom is coordinated by two N atoms from two different bipy ligands and by two I atoms in a distorted tetra­hedral geometry, with Zn—N distances ranging from 2.068 (7) to 2.101 (8) Å and Zn—I distances ranging from 2.5471 (13) to 2.5673 (13) Å. The mol­ecular structure features a zigzag polymeric chain. Face‐to‐face π–π stacking inter­actions between adjacent bipy ligands stabilize the structure.     

Poly[di‐μ‐aqua‐μ‐1,2‐bis(pyridin‐4‐yl)ethene‐κ2N:N′‐tetrakis(4‐iodobenzoato‐κ2O,O′)dicadmium]

Colourless crystals of the title compound, [Cd₂(C₇H₄IO₂)₄(C₁₂H₁₀N₂)(H₂O)₂]_n, were obtained by the self‐assembly of Cd(NO₃)₂·4H₂O, 1,2‐bis(pyridin‐4‐yl)ethene (bpe) and 4‐iodobenzoic acid (4‐IBA). Each Cd^II atom is seven‐coordinated in a pentagonal–bipyramidal coordination environment by four carboxylate O atoms from two different 4‐IBA ligands, two O atoms from two water molecules and one N atom from a bpe ligand. The Cd^II centres are bridged by the aqua molecules and bpe ligands, which lie across centres of inversion, to give a two‐dimensional net. Topologically, taking the Cd^II atoms as nodes and the μ‐aqua and μ‐bpe ligands as linkers, the two‐dimensional structure can be simplified as a (6,3) network.     

Poly[[tetraaquabis(μ2‐2‐nitroterephthalato‐κ3O1:O4,O4′)(μ2‐piperazine‐κ3N:N′)dicadmium(II)] dihydrate]

In the title complex, {[Cd₂(C₈H₃NO₆)₂(C₄H₁₀N₂)(H₂O)₄]·2H₂O}_n, the Cd^II atoms show distorted octahedral coordination. The two carboxylate groups of the dianionic 2‐nitroterephthalate ligand adopt monodentate and 1,2‐bridging modes. The piperazine molecule is in a chair conformation and lies on a crystallographic inversion centre. The Cd^II atoms are connected via three O atoms from two carboxylate groups and two N atoms from piperazine molecules to form a two‐dimensional macro‐ring layer structure. These layers are further aggregated to form a three‐dimensional structure via rich intra‐ and interlayer hydrogen‐bonding networks. This study illustrates that, by using the labile Cd^II salt and a combination of 2‐nitroterephthalate and piperazine as ligands, it is possible to generate interesting metal–organic frameworks with rich intra‐ and interlayer O—H...O hydrogen‐bonding networks.     

Poly[[μ2‐4,4′‐bipyridine‐di‐μ3‐sulfito‐dizinc(II)] monohydrate]

The title compound, {[Zn₂(SO₃)₂(C₁₀H₈N₂)]·H₂O}_n, is a two‐dimensional polymer built up of a [ZnSO₃]_n chain evolving around a 2₁ axis and inter­connected by a 4,4′‐bipyridine spacer. The resulting two‐dimensional structures are linked, in turn, by hydrogen bonding mediated by the solvent water mol­ecule. The organic ligand lies on a centre of symmetry located on the mid‐point of the bond between the rings, while the solvent water mol­ecule is halved by a twofold axis passing through the O atom.     

Poly[[diaqua(N,N‐dimethylformamide‐κO)manganese(II)]‐μ3‐sulfato]

In the title complex, [Mn(SO₄)(C₃H₇NO)(H₂O)₂]_n, each Mn^II ion has a distorted octahedral geometry formed by three O atoms of three different sulfate groups, one O atom of a dimethylformamide ligand and two water molecules. The sulfate groups act as tridentate bridging ligands connecting the Mn^II ions into a two‐dimensional layer structure which can be regraded as a 4.8² network.     

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.     

Poly[[triaquazinc(II)]‐μ3‐4‐nitrophthalato‐κ3O1:O2:O2′]

In the title complex, [Zn(C₈H₃NO₆)(H₂O)₃]_n, the two carboxylate groups of the 4‐nitrophthalate dianion ligands have monodentate and 1,3‐bridging modes, and Zn atoms are interconnected by three O atoms from the two carboxylate groups into a zigzag one‐dimensional chain along the b‐axis direction. The Zn atom shows distorted octahedral coordination as it is bonded to three O atoms from carboxylate groups of three 4‐nitrophthalate ligands and to three O atoms of three non‐equivalent coordinated water molecules. The one‐dimensional chains are aggregated into two‐dimensional layers through inter‐chain hydrogen bonding. The whole three‐dimensional structure is further maintained and stabilized by inter‐layer hydrogen bonds.     

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.     

Poly[(N,N‐dimethylformamide‐κO)(μ3‐4,4′‐ethylenedibenzoato‐κ5O,O′:O′:O′′,O′′′)(pyrazino[2,3‐f][1,10]phenanthroline‐κ2N8,N9)lead(II)]

In the title Pb^II coordination polymer, [Pb(C₁₆H₁₀O₄)(C₁₄H₈N₄)(C₃H₇NO)]_n, each Pb^II atom is eight‐coordinated by two chelating N atoms from one pyrazino[2,3‐f][1,10]phenanthroline (L) ligand, one dimethylformamide (DMF) O atom and five carboxylate O atoms from three different 4,4′‐ethylenedibenzoate (eedb) ligands. The eedb dianions bridge neighbouring Pb^II centres through four typical Pb—O bonds and one longer Pb—O interaction to form a two‐dimensional structure. The C atoms from the L and eedb ligands form C—H...O hydrogen bonds with the O atoms of eedb and DMF ligands, which further stabilize the structure. The title compound is the first Pb^II coordination polymer incorporating the L ligand.     

catena‐Poly[[aqua­(2,2′‐bipyridine‐κ2N,N′)cadmium(II)]‐μ‐4‐carboxyl­atophenoxy­acetato‐κ3O:O4,O4′]

In the title compound, [Cd(C₉H₆O₅)(C₁₀H₈N₂)(H₂O)]_n, the Cd^II atom is coordinated in a distorted octa­hedral fashion by two carboxyl­ate groups (one in a monodentate and one in a bidentate fashion) from two 4‐carboxyl­ato­phenoxy­acetate anions, two N atoms from a 2,2′‐bipyridine ligand and one aqua ligand. The structure is a helix with a long pitch of 16.441 (5) Å. A three‐dimensional supra­molecular network is further constructed through π–π stacking and hydrogen‐bonding inter­actions between the helices.     

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.     

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.     

Poly[[cobalt(II)‐di‐μ3‐3,5‐diamino­benzoato‐κ3N:N′:O] monohydrate]

In the title compound, {[Co(C₇H₇N₂O₂)₂]·H₂O}_n, the Co^II atom lies on an inversion centre and has octahedral geometry, defined by two O atoms in axial positions and four N atoms in equatorial sites from six different 3,5‐diamino­benzoate ligands. Each 3,5‐diamino­benzoate anion acts as a μ₃‐bridging ligand, linking three adjacent Co^II ions through one O atom and two N atoms to form a three‐dimensional coordination polymer.     

catena‐Poly[[diaqua­bis(5‐carboxy­pentan­oato‐κO)cobalt(II)]‐μ‐1,2‐di‐4‐pyridylethane‐κ2N:N′]

The title compound, [Co(C₆H₉O₄)₂(C₁₂H₁₂N₂)(H₂O)₂]_n, crystallizes in the space group P. The Co atom is on a center of symmetry and the 1,2‐di‐4‐pyridylethane (bpe) ligand also sits across a crystallographic inversion center. The Co atom is octa­hedrally coordinated by two aqua ligands, two carboxyl­ate O atoms and two pyridyl N atoms, and is bridged by the anti‐bpe ligands to generate one‐dimensional {[Co(Hadip)₂(H₂O)₂](bpe)_2/2} chains (Hadip is 5‐carboxypentanoate), which are further inter­linked by O—H⋯O and C—H⋯O hydrogen bonds into two‐dimensional layers.     

Poly[[diaqua­cadmium(II)]‐μ4‐[N‐(phosphonato­methyl)ammonio]acetato]

The title compound, [Cd(C₃H₆NO₅P)(H₂O)₂]_n, is a three‐dimensional polymeric complex. The asymmetric unit contains one Cd atom, one N‐(phosphono­methyl)glycine zwitterion [(O⁻)₂OPCH₂NH₂⁺CH₂COO⁻] and two water mol­ecules. The coordination geometry is a distorted CdO₆ octa­hedron. Each N‐(phosphono­methyl)glycine ligand bridges four adjacent water‐coordinated Cd cations through three phospho­nate O atoms and one carboxyl­ate O atom, like a regular PO₄³⁻ group in zeolite‐type frameworks. One‐dimensional zigzag (–O—P—C—N—C—C—O—Cd–)_n chains along the [101] direction are linked to one another via Cd—O—P bridges and form a three‐dimensional network motif with three types of channel systems. The variety of O—H⋯O and N—H⋯O hydrogen bonds is likely to be responsible for stabilizing the three‐dimensional network structure and preventing guest mol­ecules from entering into the channels.     

catena‐Poly[[dicyanamido(5,5′‐dimethyl‐2,2′‐bipyridine‐κ2N,N′)copper(II)]‐μ‐dicyanamido‐κ2N1:N5]

In the crystal structure of the title compound, [Cu(C₂N₃)₂(C₁₂H₁₂N₂)]_n, the Cu^II atom adopts a distorted square‐pyramidal geometry, the basal plane of which is formed by two N atoms of the bi­pyridine ligand, one N atom of a bidentate dicyan­amide anion and one N atom of a monodentate dicyan­amide anion [Cu—N = 1.9760 (15)–2.0157 (15) Å]. The apical position is occupied by an N atom of a bidentate dicyan­amide anion, located 2.2468 (16) Å from the Cu atom, thus forming a one‐dimensional polymeric chain.     

μ2‐Acetato‐κ2O:O′‐tris(μ2‐ferrocenecarboxylato‐κ2O:O′)bis[(N,N‐dimethylformamide‐κO)copper(II)]

The title compound, [Cu₂Fe₃(C₅H₅)₃(C₂H₃O₂)(C₆H₄O₂)₃(C₃H₇NO)₂], belongs to the classic dimeric paddle‐wheel structure type. It is an unusual example in that it contains two different carboxylate groups, viz. ferrocenecarboxylate and acetate. With three ferrocenecarboxylate groups and only one acetate group bridging the two Cu centres, a noncentrosymmetric molecular arrangement results.