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.     

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.     

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[[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.     

Bis(μ‐2‐sulfonatobenzoato)bis[(1,10‐phenanthroline)­lead(II)] dihydrate

In the title centrosymmetric dimer, [Pb₂(sbc)₂(phen)₂]·2H₂O [sbc is the 2‐sulfonatobenzoate dianion (C₇H₄O₅S) and phen is 1,10‐phenanthroline (C₁₂H₈N₂)], each Pb^II ion is six‐coordinated by four O atoms, viz. carboxyl­ate and sulfonate O atoms from two sbc anions, and two N atoms from a 1,10‐phenanthroline ligand. One 1,10‐phenanthroline ligand and the carboxyl­ate group of one sbc ligand are chelated to each Pb^II cation, and the sulfonate group of the other sbc unit is monodentate. One O atom of the chelated carboxyl­ate group also bridges to the other Pb^II cation, so that each pair of Pb^II ions is bridged by two sbc anions and has the same coordination environment, forming a dinuclear ring. Each pair of Pb^II ions is thus connected by two different kinds of bridges, namely a carboxyl­ate short bridge and a carboxyl­ate–sulfonate long bridge. There is also a special position of site symmetry at the centre of the two Pb^II cations.     

catena‐Poly[[silver(I)‐μ‐[(E)‐1,2‐bis(2‐pyridyl)ethylene‐N:N′]] nitrate]

In the title complex, {[Ag(C₁₂H₁₀N₂)]NO₃}_n, the Ag atom, which is in a linear AgN₂ geometry, is surrounded by two trans‐related N atoms of two bpe ligands [Ag—N = 2.173 (3) and 2.176 (3) Å; bpe is trans‐1,2‐bis(2‐pyridyl)­ethyl­ene]. The bpe ligands bridge neighbouring Ag atoms to form zigzag polymeric chains in the lattice. These adjacent one‐dimensional zigzag chains are extended into a three‐dimensional supramolecular array by strong interchain π?π interactions between the pyridyl rings of adjacent chains.     

A three‐dimensional ZnII coordination framework: poly[[μ2‐(E)‐1,2‐bis(pyridin‐4‐yl)ethene][μ4‐(E)‐2,2′‐(diazene‐1,2‐diyl)dibenzoato][μ2‐(E)‐2,2′‐(diazene‐1,2‐diyl)dibenzoato]dizinc(II)]

In the title coordination polymer, [Zn₂(C₁₄H₈N₂O₄)₂(C₁₂H₁₀N₂)]_n, the asymmetric unit contains one Zn^II cation, two halves of 2,2′‐(diazene‐1,2‐diyl)dibenzoate anions (denoted L²⁻) and half of a 1,2‐bis(pyridin‐4‐yl)ethene ligand (denoted bpe). The three ligands lie across crystallographic inversion centres. Each Zn^II centre is four‐coordinated by three O atoms of bridging carboxylate groups from three L²⁻ ligands and by one N atom from a bpe ligand, forming a tetrahedral coordination geometry. Two Zn^II atoms are bridged by two carboxylate groups of L²⁻ ligands, generating a [Zn₂(CO₂)₂] ring. Each loop serves as a fourfold node, which links its four equivalent nodes via the sharing of four L²⁻ ligands to form a two‐dimensional [Zn₂L₄]_n net. These nets are separated by bpe ligands acting as spacers, producing a three‐dimensional framework with a 4⁶6⁴ topology. Powder X‐ray diffraction and solid‐state photoluminescence were also measured.     

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[[diaquadiisothiocyanatoiron(II)]‐μ‐4,4′‐bi‐1,2,4‐triazole]: a one‐dimensional coordination polymer

In the title complex, [Fe(NCS)₂(C₄H₂N₆)₂(H₂O)₂]_n, the Fe^II atom is on an inversion centre and the 4,4′‐bi‐1,2,4‐triazole (btr) group is bisected by a twofold axis through the central N—N bond. The coordination geometry of the Fe^II atom is elongated distorted FeN₄O₂ octahedral, where the cation is coordinated by two N atoms from the triazole rings of two btr groups, two N atoms from NCS⁻ ligands and two water molecules. Btr is a bidentate ligand, coordinating one Fe^II atom through a peripheral N atom of each triazole ring, leading to a one‐dimensional polymeric (chain) structure extending along [101]. The chains are further connected through a network of O—H...N and C—H...S hydrogen bonds.     

The three‐dimensional coordination polymer poly[[aqua[μ4‐2,2′‐(diazene‐1,2‐diyl)dibenzoato]lead(II)] 1,2‐bis(pyridin‐4‐yl)ethylene hemisolvate]

A novel three‐dimensional coordination polymer, {[Pb(C₁₄H₈N₂O₄)(H₂O)]·0.5C₁₂H₁₀N₂}_n, has been synthesized by hydrothermal reaction of Pb(OAc)₂·3H₂O (OAc is acetate), 2,2′‐(diazene‐1,2‐diyl)dibenzoic acid (H₂L) and 1,2‐bis(pyridin‐4‐yl)ethylene (bpe). The asymmetric unit contains a crystallographically independent Pb^II cation, one L²⁻ ligand, an aqua ligand and half a bpe molecule. Each Pb^II centre is seven‐coordinated by six O atoms of bridging–chelating carboxylate groups from L²⁻ ligands and by one O atom from a coordinated water molecule. The Pb^II cations are bridged by L²⁻ ligands, forming [PbO₂]_n chains along the a axis. These chains are further connected by L²⁻ ligands along the b and c axes to give a three‐dimensional framework with a 4¹²6³ topology. The channel voids are occupied by bpe molecules.     

A three‐dimensional cadmium(II) coordination polymer: poly[[[μ‐4,4′‐(propane‐1,3‐diyl)dipyridine‐κ2N:N](μ‐3,3′‐thiodipropionato‐κ3O,O′:O)cadmium(II)] monohydrate]

In the title coordination polymer, {[Cd(C₆H₈O₄S)(C₁₃H₁₄N₂)]·H₂O}_n, the Cd^II atom displays a distorted octahedral coordination, formed by three carboxylate O atoms and one S atom from three different 3,3′‐thiodipropionate ligands, and two N atoms from two different 4,4′‐(propane‐1,3‐diyl)dipyridine ligands. The Cd^II centres are bridged through carboxylate O atoms of 3,3′‐thiodipropionate ligands and through N atoms of 4,4′‐(propane‐1,3‐diyl)dipyridine ligands to form two different one‐dimensional chains, which intersect to form a two‐dimensional layer. These two‐dimensional layers are linked by S atoms of 3,3′‐thiodipropionate ligands from adjacent layers to form a three‐dimensional network.     

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 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 three‐dimensional metal–organic polymer: poly[bis(μ2‐pyrimidine‐2‐thiolato‐κ4N1,S:S,N3)lead(II)]

The title compound, [Pb(C₄H₃N₂S)₂]_n, was prepared by the reaction of [Pb(OAc)₂]·3H₂O (OAc is acetate) with pyrimidine‐2‐thione in the presence of triethylamine in methanol. In the crystal structure, the Pb^II atom has an N₄S₄ coordination environment with four ligands coordinated by N‐ and S‐donor atoms. This compound shows that the pyrimidine‐2‐thiolate anion can lead to a three‐dimensional network when the coordination number of the metal ion can be higher than 6, as is the case with the Pb^II ion. This compound presents only covalent bonds, showing that despite the possibility of the hemidirected geometries of Pb^II, the eight‐coordinated ion does not allow the formation of an isolated molecular structure with pyrimidine‐2‐thiolate as the ligand.     

A novel two‐dimensional zinc(II) coordination polymer with 6‐mercaptonicotinic acid

The novel title Zn^II coordination polymer, poly[bis(μ‐6‐thioxo‐1,6‐dihydropyridine‐3‐carboxylato‐κ²S:O)zinc(II)], [Zn(C₆H₄NO₂S)₂]_n, consists of two crystallographically independent zinc centers and two 6‐mercaptonicotinate (Hmna⁻) ligands. Each Zn^II atom is four‐coordinated and lies at the center of a distorted tetrahedral ZnS₂O₂ coordination polyhedron, bridged by four Hmna⁻ ligands to form a two‐dimensional (4,4)‐network. Each Hmna⁻ ion acts as a bridging bidentate ligand, coordinating to two Zn^II atoms through the S atom and a carboxyl O atom. The metal centers reside on twofold rotation axes. The coordination mode of the S atoms and N—H...O hydrogen‐bonding interactions between the protonated N atoms and the uncoordinated carboxyl O atoms give the extended structure a wavelike form.     

The two‐dimensional coordination polymer poly[diaqua(μ2‐1H‐imidazo[4,5‐f][1,10]phenanthroline)‐μ4‐sulfato‐μ3‐sulfato‐dicadmium(II)]

In the title coordination polymer, [Cd₂(SO₄)₂(C₁₃H₈N₄)(H₂O)₂]_n, there are two crystallographically independent Cd^II centres with different coordination geometries. The first Cd^II centre is hexacoordinated by four O atoms of four sulfate ligands, one water O atom and one N atom of a 1H‐imidazo[4,5‐f][1,10]phenanthroline (IP) ligand, giving a distorted octahedral coordination environment. The second Cd^II centre is heptacoordinated by four O atoms of three sulfate ligands, one water O atom and two N atoms of one chelating IP ligand, resulting in a distorted monocapped anti‐trigonal prismatic geometry. The symmetry‐independent Cd^II ions are bridged in an alternating fashion by sulfate ligands, forming one‐dimensional ladder‐like chains which are connected through the IP ligands to form two‐dimensional layers. These two‐dimensional layers are linked by interlayer hydrogen bonds, leading to the formation of a three‐dimensional supramolecular network.     

(2‐Aminopyrimidine‐κN1)aqua(pyridine‐2,6‐dicarboxylato‐κ3O2,N,O6)copper(II): X‐ray and DFT calculated structure

In the title compound, [Cu(C₇H₃N₂O₄)(C₄H₅N₂)(H₂O)], (I), pyridine‐2,6‐dicarboxylate (pydc²⁻), 2‐aminopyrimidine and aqua ligands coordinate the Cu^II centre through two N atoms, two carboxylate O atoms and one water O atom, respectively, to give a nominally distorted square‐pyramidal coordination geometry, a common arrangement for copper complexes containing the pydc²⁻ ligand. Because of the presence of Cu...X_bridged contacts (X = N or O) between adjacent molecules in the crystal structures of (I) and three analogous previously reported compounds, and the corresponding uncertainty about the effective coordination number of the Cu^II centre, density functional theory (DFT) calculations were used to elucidate the degree of covalency in these contacts. The calculated Wiberg and Mayer bond‐order indices reveal that the Cu...O contact can be considered as a coordination bond, whereas the amine group forming a Cu...N contact is not an effective participant in the coordination environment.     

Poly[bis(μ‐4‐benzoyl‐1‐isonicotinoylthiosemicarbazide‐κ2N:S)dichloridocadmium(II)]

The asymmetric unit of the title complex, [CdCl₂(C₁₄H₁₂N₄O₂S)₂]_n, consists of one Cd^II ion located on the crystallographic inversion centre, one 4‐benzoyl‐1‐isonicotinoylthiosemicarbazide ligand and one chloride ligand. The central Cd^II ion adopts a distorted octahedral coordination geometry formed by two pyridyl N atoms of two ligands, two S atoms of two other ligands and two chloride ligands. The thiosemicarbazide ligands act as bridges, linking the metal ions into a two‐dimensional layered structure parallel to the bc plane. Intermolecular N—H...O hydrogen bonds and C—H...π interactions exist between adjacent layers.     

An unusual chain cadmium(II) coordination polymer: catena‐poly[[(2,2′‐bipyridyl‐κ2N,N′)cadmium(II)]‐di‐μ‐chlorido‐[(2,2′‐bipyridyl‐κ2N,N′)cadmium(II)]‐di‐μ‐thiocyanato‐κ2N:S;κ2S:N]

The title complex, [CdCl(NCS)(C₁₀H₈N₂)]_n, represents an unusual Cd^II coordination polymer constructed by two types of anionic bridges and 2,2′‐bipyridyl (bipy) terminal ligands. These two types of bridges are arranged around inversion centers. The distorted octahedral coordination of the Cd^II center is provided by two chloride ions, one N‐ and one S‐donor atom from two thiocyanate ions, and a pair of N atoms from the chelating bipy ligand. Interestingly, adjacent Cd^II ions are interconnected alternately by paired chloride [Cd...Cd = 3.916 (1) Å] and thiocyanate bridges [Cd...Cd = 5.936 (1) Å] to generate an infinite one‐dimensional coordination chain. Furthermore, weak interchain C—H...S interactions between the bipy components and thiocyanate ions lead to the formation of a layered supramolecular structure.     

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.