Poly[(μ2‐aqua‐κ2O:O)(μ3‐azido‐κ3N1:N1:N3)(μ2‐isonicotinato‐κ2O:O′)lead(II)]

In the title compound, [Pb(C₆H₄NO₂)(N₃)(H₂O)]_n, the Pb ion is seven‐coordinated by three N atoms from three azide ligands, two O atoms from two isonicotinate (inic) ligands and two O atoms from two coordinated water molecules, forming a distorted monocapped triangular prismatic coordination geometry. Each azide ligand bridges three Pb^II ions in a μ_1,1,3 coordination mode to form a two‐dimensional three‐connected 6³ topology network extending in the bc plane. The carboxylate group of the inic unit and the aqua ligand act as coligands to bridge Pb^II ions. Adjacent two‐dimensional layers are connected by hydrogen‐bonding interactions between the isonicotinate N atom and the water molecule, resulting in an extended three‐dimensional network. The title complex is the first reported coordination polymer involving a p‐block metal, an azide and a carboxylate.     

catena‐Poly[[aqua(11‐chloropyrido[2′,3′:2,3]pyrimidino[5,6‐f][1,10]phenanthroline‐κ2N4,N5)cadmium(II)]‐μ‐benzene‐1,4‐dicarboxylato‐κ3O1,O1′:O4]: an inclined interpenetrating (6,3) network

The asymmetric unit of the title compound, [Cd(C₈H₄O₄)(C₁₇H₈ClN₅)(H₂O)]_n, contains one Cd^II atom, two half benzene‐1,4‐dicarboxylate (1,4‐bdc) anions, one 11‐chloropyrido[2′,3′:2,3]pyrimidino[5,6‐f][1,10]phenanthroline (L) ligand and one coordination water molecule. The 1,4‐bdc ligands are on inversion centers at the centroids of the arene rings. The Cd^II atom is six‐coordinated by two N atoms from one L ligand, three carboxylate O atoms from two different 1,4‐bdc ligands and one water O atom in a distorted octahedral coordination sphere. Each Cd^II center is bridged by the 1,4‐bdc dianions to give a one‐dimensional chain. π–π stacking interactions between L ligands of neighboring chains extend adjacent chains into a two‐dimensional supramolecular (6,3) network. Neighboring (6,3) networks are interpenetrated in an unusual inclined mode, resulting in a three‐dimensional framework. Additionally, the water–carboxylate O—H...O hydrogen bonds observed in the network consolidate the interpenetrating nets.     

catena‐Poly[[diaquabis(2‐chloronicotinato‐κ2O,O′)cadmium(II)]‐μ‐2‐chloronicotinato‐κ3O,O′:N]

In the title neutral coordination polymer, [Cd(C₆H₃ClNO₂)₂(H₂O)₂]_n, each Cd^II ion is coordinated by one N and four O atoms from three 2‐chloro­nicotinate ligands and by two aqua ligands, defining a distorted monocapped octahedral coordination geometry. Adjacent Cd atoms are linked by the pyridyl N atom and the bidentate carboxyl­ate functional group of a 2‐­chloro­nicotinate ligand, forming a one‐dimensional infinite chain along the b axis. The Cd⋯Cd distance is 8.112 (3) Å. These chains are linked by O—H⋯O and O—H⋯N hydrogen bonds into a three‐dimensional network structure.     

catena‐Poly[[aquacopper(II)]‐μ‐hydroxido‐μ‐naphthalene‐1‐carboxylato‐κ2O:O′]: effect of a bulky aromatic skeleton in self‐assembly

In the title coordination polymer, [Cu(C₁₁H₇O₂)(OH)(H₂O)]_n, the Cu^II center is five‐coordinated by two O atoms from two different naphthalene‐1‐carboxylate (L) ligands, one O atom from one coordinated water molecule and two O atoms from two hydroxide anions. L ligands and hydroxide anions jointly bridge adjacent Cu^II centers to generate a one‐dimensional chain along the b‐axis direction. The results reveal that the steric bulk of the naphthalene ring system in L may play an important role in the formation of the title complex.     

catena‐Poly[[nickel(II)‐μ2‐[1,3‐bis(imidazol‐1‐ylmethyl)benzene‐κ2N3:N3′]‐μ2‐(5‐carboxybenzene‐1,3‐dicarboxylato‐κ4O1,O1′:O3,O3′)] 0.41‐hydrate]

The title compound, {[Ni(C₉H₄O₆)(C₁₄H₁₄N₄)]·0.41H₂O}_n, exhibits a three‐dimensional hydrogen‐bonded supramolecular framework. The Ni^II cation is six‐coordinated in a distorted triangular prism defined by two N atoms from two 1,3‐bis(imidazol‐l‐ylmethyl)benzene (bix) ligands and four O atoms from two 5‐carboxybenzene‐1,3‐dicarboxylate (HBTC) dianions. The bix molecules and HBTC dianions both act as bidentate ligands, linking the Ni^II cations to form a one‐dimensional coordination polymer. A two‐dimensional wave‐like net is constructed by O—H...O hydrogen bonds linking adjacent chains. Partially occupied solvent water molecules fill the cavities and link these layers to form a three‐dimensional supramolecular structure via O—H...O hydrogen bonds. The title compound was also characterized by powder X‐ray diffraction and thermogravimetric analysis.     

A bicapped trigonal–prismatic lead complex: catena‐poly[[[aqua­bis(1,10‐phenanthroline‐κ2N,N′)lead(II)]‐μ‐squarato‐κO1:κ2O2,O3] dihydrate]

The asymmetric unit of the title compound, {[Pb(C₄O₄)(C₁₂H₈N₂)₂(H₂O)]·2H₂O}_n, contains one squarate dianion, two phenanthroline (phen) ligands and one aqua ligand all coordinated to Pb, and two solvent water mol­ecules. The eight‐coordinate Pb metal ion displays a distorted bicapped trigonal–prismatic coordination environment, defined by three squarate O atoms, four N atoms from two chelating phen ligands and one O atom from the coordinated water mol­ecule. The crystal structure contains chains of squarate‐1,2,3‐bridged Pb^II ions running in the [010] direction. These polymeric chains are linked to one another via offset face‐to‐face π–π inter­actions between the phen ligands, which lead to a two‐dimensional network extending along the (001) plane. The crystal structure is also stabilized by O—H⋯O inter­molecular hydrogen‐bond inter­actions, forming a three‐dimensional network.     

Helical catena‐poly[[tris(1H‐benzimidazole‐κN3)cobalt(II)]‐μ‐maleato‐κ3O,O′:O′′]

The crystal structure of the title compound, [Co(C₄H₂O₄)(C₇H₆N₂)₃]_n, consists of polymeric chains of the Co^II complex. Two maleate dianions and three benz­imidazole ligands coordinate to the Co^II atom with a distorted octahedral geometry. The maleate dianions bridge neighbouring Co^II atoms via both terminal carboxylic acid groups, one of which is monodentate and the other bidentate, to form a helical structure of alternating maleate dianions and Co^II atoms, with a pitch height of 9.2667 (17) Å. The absolute structure has been determined, and the crystal contains only right‐handed helices. Intrahelical N—H⋯O hydrogen bonds stabilize the helical structure, while interhelical N—H⋯O hydrogen bonds link neighbouring helices to form the supramolecular structure.     

Poly[[[aqua­(2,2′‐bipyridine‐κ2N,N′)manganese(II)]‐μ3‐acetyl­enedicarboxylato‐κ3O:O′:O′′] monohydrate]

In the title complex, {[Mn(C₄O₄)(C₁₀H₈N₂)(H₂O)]·H₂O}_n, each Mn^II ion has a distorted octa­hedral coordination formed by two N atoms of a 2,2′‐bipyridine ligand, three carboxyl O atoms of three different acetyl­ene­dicarboxyl­ate ligands and one coordinated water mol­ecule. The acetyl­ene­dicarboxyl­ate ligands act in a tridentate mode connecting adjacent Mn^II ions and constructing a two‐dimensional structure which can be regarded as an unusual plywood‐like stacked network.     

A capped trigonal prismatic cadmium complex with tetra‐ and tridentate ligands: bis­(tri­ethanol­amine)‐κ3N,O,O′;κ4N,O,O′,O′′‐cadmium(II) squarate monohydrate

In the crystal structure of the title compound, [Cd(C₆H₁₅NO₃)₂](C₄O₄)·H₂O, a supramolecular structure is observed. The asymmetric unit consists of one unit of the cationic Cd complex, one water mol­ecule and two half‐squarate anions, each sitting on a crystallographic inversion center. The different coordinations of the two triethanolamine (TEA) ligands results in an unusual example of coordination number seven for the Cd^II ion. Both TEA ligands coordinate to the Cd^II ion, forming a distorted monocapped trigonal prismatic geometry with approximate C_2v symmetry. One of the TEA ligands acts as an N,O,O′‐tridentate ligand, whereas the other behaves as an N,O,O′,O′′‐tetradentate donor. The anions and cations are linked to one another by hydrogen bonds between hydroxy H atoms of the TEA ligands and squarate O atoms. The crystal structure is stabilized by O—H⋯O hydrogen bonds between the unligated water mol­ecule and a squarate O atom, together with a weak π–ring interaction between the ethyl­ene group of a TEA ligand and a squarate anion.     

A new potential NLO compound with a supramolecular layered structure: aqua(hexamethylenetetramine‐κN)(iminodiacetato‐κ3O,N,O′)copper(II)

In the noncentrosymmetric title compound, [Cu(C₄H₅NO₄)(C₆H₁₂N₄)(H₂O)] or [Cu(IDA)(HMTA)(H₂O)], where IDA is iminodiacetate and HMTA is hexamethylenetetramine, the asymmetric unit consists of a whole mononuclear neutral molecule, where the Cu^II cation is coordinated by two carboxylate O atoms and one N atom from the IDA ligand, by one N atom from the HMTA ligand and by the O atom of the coordinated water molecule, giving rise to a CuN₂O₃ distorted square‐pyramidal coordination geometry. The IDA and HTMA ligands adopt terminal tri‐ and monocoordinated modes, respectively. All adjacent molecules within the ac plane are connected to each other via two pairs of O—H...O and one N—H...O hydrogen bond, forming a (4,4) supramolecular two‐dimensional network. In the unit cell, these layers stack alternately in an …ABABAB… sequence along the b axis. The optical absorption properties of this compound have been studied on powder samples, which had previously been examined by powder X‐ray diffraction.     

catena‐Poly­[[aqua(2,2′‐bi­pyridine‐κ2N,N′)­manganese(II)]‐μ‐terephthalato‐κ3O,O′:O′′]

The title complex, [Mn(C₈H₄O₄)(C₁₀H₈N₂)(H₂O)]_n, takes the form of a zigzag chain, with the terephthalate dianion (tp) acting as a tridentate ligand. The Mn^II center is surrounded by two tp ligands, one water mol­ecule and one 2,2′‐bi­pyridine (bipy) ligand and exhibits a severely distorted octahedral coordination environment, with cis angles ranging from 57.31 (8) to 123.97 (11)°. The complete solid‐state structure can be described as a three‐dimensional supramolecular framework stabilized by hydrogen‐bonding interactions involving the coordinated water mol­ecule and the carboxy O atoms of the tp ligands, and by π–π stacking interactions involving the bipy rings and the benzene ring of the tp ligand.     

catena‐Poly­[[bis­(thio­cyanato‐N)lead(II)]‐μ‐1,2‐bis(4‐pyridyl)ethane‐N:N′]

In the title coordination polymer, [Pb(NCS)₂(C₁₂H₁₂N₂)], the coordination geometry about the Pb^II atom is a distorted octahedron, composed of two N atoms from bpe ligands [bpe is 1,2‐bis(4‐pyridyl)ethane], two other N atoms from NCS^? groups and two neighbouring S atoms through short contacts. The trans‐bpe ligands act as bridges between two Pb^II centres resulting in the formation of a linear chain. The terminal S atoms of the NCS^? ligands make short contacts with the Pb^II atom of neighbouring chains to form an infinite two‐dimensional polymeric structure.     

Aqua(dipicolinato‐κ3O,N,O′)(1H‐imidazole‐κN3)(1,10‐phenanthroline‐N,N′)manganese(II)

In the title compound, [Mn(C₇H₃NO₄)(C₃H₄N₂)(C₁₂H₈N₂)(H₂O)], the Mn^II centre is surrounded by one bidentate phenanthroline ligand [Mn—N = 2.383 (3) and 2.421 (3) Å], one tridentate dipicolinate ligand [Mn—N = 2.300 (3) Å, and Mn—O = 2.300 (2) and 2.357 (2) Å], one monodentate imidazole ligand [Mn—N = 2.238 (3) Å] and one water molecule [Mn—O = 2.157 (3) Å]. It displays a distorted pentagonal‐bipyramidal geometry, with neighbouring angles within the equatorial plane ranging from 68.05 (9) to 77.48 (10)°. Intermolecular O—H...O hydrogen bonds link the molecules into infinite chains. The chains are crosslinked by hydrogen bonds involving the carboxyl O atoms of the dipicolinate ligand and the protonated imidazole N atom, leading to an infinite two‐dimensional network sheet packing mode. The complete solid‐state structure can be described as a three‐dimensional supramolecular framework, stabilized by these intermolecular hydrogen‐bonding interactions and π–π stacking interactions involving the phenanthroline rings.     

Poly[diaqua(μ4‐benzene‐1,2‐dicarboxylato)(isonicotinato‐κ2O,O′)gadolinium(III)]

The title neutral polymer, [Gd(C₆H₄NO₂)(C₈H₄O₄)(H₂O)₂]_n, contains an extended two‐dimensional wave‐like lanthanide carboxylate layer decorated by isonicotinate (IN) ligands. The Gd^II atom is eight‐coordinated by four carboxylate O atoms from four benzene‐1,2‐dicarboxylate (1,2‐bdc) ligands, two 1,2‐bdc carboxylate O atoms from one chelating IN ligand and two terminal water molecules, forming a bicapped trigonal–prismatic coordination geometry. The wave‐like layers are stacked in an …ABAB… packing mode along the c‐axis direction. Strong hydrogen‐bonding interactions further stabilize the structure of the title compound.     

A two‐dimensional manganese(II) coordination polymer: poly­[[di­aqua­manganese(II)]‐μ‐4,4‐bi­pyridine‐κ2N:N′‐μ‐(p‐phenyl­ene­dioxy­diacetato)‐κ2O:O′]

In the title two‐dimensional coordination polymer, [Mn(1,4‐BDOA)(4,4‐bipy)(H₂O)₂]_n [1,4‐BDOA²⁻ is the p‐phenyl­ene­dioxy­di­acetate dianion (C₁₀H₈O₆) and 4,4‐bipy is 4,4‐bi­pyridine (C₁₀H₈N₂)], each Mn^II atom displays octahedral coordination by two O atoms of the 1,4‐BDOA²⁻ groups, two N atoms of the 4,4‐bipy ligands and two solvent water mol­ecules. The Mn^II atom, 4,4‐bipy ligand and 1,4‐BDOA²⁻ group occupy different inversion centres. Adjacent Mn^II atoms are bridged by 1,4‐BDOA²⁻ groups and 4,4‐bipy ligands, forming a two‐dimensional network with Mn⋯Mn separations of 11.592 (2) and 11.699 (2) Å. Hydro­gen bonds from a water O—H group link the layers in the third dimension.     

Poly[aqua[μ3‐(pyridin‐1‐ium‐3,5‐diyl)diphosphonato‐κ3O:O′:O′′][μ2‐(pyridin‐1‐ium‐3,5‐diyl)diphosphonato‐κ2O:O′]calcium(II)]

The rigid organic ligand (pyridine‐3,5‐diyl)diphosphonic acid has been used to create the title novel three‐dimensional coordination polymer, [Ca(C₅H₆NO₆P₂)₂(H₂O)]_n. The six‐coordinate calcium ion is in a distorted octahedral environment, formed by five phosphonate O atoms from five different (pyridin‐1‐ium‐3,5‐diyl)diphosphonate ligands, two of which are unique, and one water O atom. Two crystallographically independent acid monoanions, L1 and L2, serve to link metal centres using two different coordination modes, viz.η²μ₂ and η³μ₃, respectively. The latter ligand, L2, forms a strongly undulated two‐dimensional framework parallel to the crystallographic bc plane, whereas the former ligand, L1, is utilized in the formation of one‐dimensional helical chains in the [010] direction. The two sublattices of L1 and L2 interweave at the Ca²⁺ ions to form a three‐dimensional framework. In addition, multiple O—H...O and N—H...O hydrogen bonds stabilize the three‐dimensional coordination network. Topologically, the three‐dimensional framework can be simplified as a very unusual (2,3,5)‐connected three‐nodal net represented by the Schläfli symbol (4·8²)(4·8⁸·10)(8).     

Poly[aqua[μ2‐1,4‐bis(imidazol‐1‐ylmethyl)benzene‐κ2N3:N3′](μ2‐5‐hydroxybenzene‐1,3‐dicarboxylato‐κ4O1,O1′:O3,O3′)cadmium(II)], a twofold interpenetrated CdSO4‐like metal–organic polymer

In the title cadmium(II) complex, [Cd(C₈H₄O₅)(C₁₄H₁₄N₄)(H₂O)]_n, the 5‐hydroxybenzene‐1,3‐dicarboxylate (5‐OH‐1,3‐bdc) and 1,4‐bis(imidazol‐1‐ylmethyl)benzene (1,4,‐bix) ligands bridge water‐coordinated Cd^II atoms to generate a three‐dimensional network. Two carboxylate groups from different ligands function as O,O′‐chelates, while two imidazole N atoms from different ligands coordinate in a monodentate fashion, and one water molecule completes the seven‐coordinate pentagonal bipyramid around the Cd^II atom, in which the N atoms occupy the axial sites and the O atoms occupy the equatorial sites. The overall architecture is a twofold interpenetrated CdSO₄‐type framework. The two crystallographically equivalent frameworks are linked by O—H...O hydrogen bonds between the water, hydroxy and carboxylate groups.     

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.     

(2,2′‐Bipyridyl‐κ2N,N′)­bis­(salicyl­ato‐κ2O,O′)­zinc(II)

The asymmetric unit of the title compound, [Zn(C₇H₅O₃)₂(C₁₀H₈N₂)], contains one monomeric zinc complex. The Zn atom is coordinated to one 2,2′‐bipyridyl ligand via both N atoms and to two salicyl­ate anions (Hsal⁻) in a bidentate chelating manner involving carboxyl­ate O‐atom coordination. The complex exhibits a distorted octahedral geometry about the Zn^II atom, with the `apical' positions occupied by one of the two N atoms of the bipyridyl ligand and an O atom from one Hsal<sup>−</sup> ligand; the Zn atom is 0.168 (1) Å out of the `basal' plane. Two intramolecular six‐membered hydrogen‐bonded rings are present, generated from interactions between the carboxyl and hydroxyl groups of the salicyl­ate ligands. The crystal packing is governed by weak C—H⋯O and C—H⋯π interactions.     

Poly[triaqua(μ4‐4‐carboxybenzenesulfonato‐κ4O:O′:O′′:O′′′)(4‐carboxybenzenesulfonato‐κO)strontium(II)]

This study presents the coordination modes and two‐dimensional network of a novel strontium(II) coordination polymer, [Sr(C₇H₅O₅S)₂(H₂O)₃]_n. The eight‐coordinate Sr²⁺ ion is in a distorted bis‐disphenoidal coordination environment, surrounded by four sulfonate and one carboxyl O atom from five benzenesulfonate ligands, two of which are symmetry unique, and by three O atoms from three independent aqua ligands. The compound exhibits a monolayer structure with coordination bonds within and hydrogen bonds between the layers. The μ₄ acid ligand bridges the metal ions in two dimensions to form a thick undulating monolayer with a hydrophobic interior and hydrophilic surfaces. A second independent monoanion is arranged outward from both sides of the monolayer and serves to link adjacent monolayers via carboxyl–water and water–carboxyl hydrogen bonds.