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.     

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.     

(1,3‐Dimethylimidazolidine‐2‐selone‐κSe)bis(1,10‐phenanthroline‐κ2N,N′)copper(II) bis(perchlorate) and bis(2,2′‐bipyridyl‐κ2N,N′)(imidazolidine‐2‐thione‐κS)copper(II) bis(perchlorate)

In the first title salt, [Cu(C₁₂H₈N₂)₂(C₅H₁₀N₂Se)](ClO₄)₂, the Cu^II centre occupies a distorted trigonal–bipyramidal environment defined by four N donors from two 1,10‐phenanthroline (phen) ligands and by the Se donor of a 1,3‐dimethylimidazolidine‐2‐selone ligand, with the equatorial plane defined by the Se and by two N donors from different phen ligands and the axial sites occupied by the two remaining N donors, one from each phen ligand. The Cu—N distances span the range 1.980 (10)–2.114 (11) Å and the Cu—Se distance is 2.491 (3) Å. Intermolecular π–π contacts between imidazolidine rings and the central rings of phen ligands generate chains of cations. In the second salt, [Cu(C₁₀H₈N₂)₂(C₃H₆N₂S)](ClO₄)₂, the Cu^II centre occupies a similar distorted trigonal–bipyramidal environment comprising four N donors from two 2,2′‐bipyridyl (bipy) ligands and an S donor from an imidazolidine‐2‐thione ligand. The equatorial plane is defined by the S donor and two N donors from different bipy ligands. The Cu—N distances span the range 1.984 (6)–2.069 (7) Å and the Cu—S distance is 2.366 (3) Å. Intermolecular π–π contacts between imidazolidine and pyridyl rings form chains of cations. A major difference between the two structures is due to the presence in the second complex of two N—H...O hydrogen bonds linking the imidazolidine N—H hydrogen‐bond donors to perchlorate O‐atom acceptors.     

catena‐Poly­[[di­aqua­cadmium(II)]‐μ‐5‐carboxyimidazole‐4‐carboxylato‐κ4N1,O5:O4,N3]

A new cadmium coordination polymer, [Cd(C₅H₂N₂O₄)(H₂O)₂]_n, possesses a one‐dimensional zigzag chain structure built from Cd^II centers bridged sequentially by pairs of O and N atoms of the 5‐carboxyimidazole‐4‐carboxylate ligand. The Cd^II center is in a distorted octahedral geometry, being coordinated by two O atoms from two coordinated water mol­ecules [Cd—O = 2.322 (7) and 2.364 (7) Å], and by two N atoms [Cd—N = 2.222 (6) and 2.232 (6) Å] and two carboxyl O atoms [Cd—O = 2.383 (6) and 2.414 (6) Å] from two 5‐carboxyimidazole‐4‐carboxylate ligands.     

Poly[diaquabis(μ‐4,4′‐bipyridine‐κ2N:N′)bis(ethane‐1,2‐diol)di‐μ‐sulfato‐dicopper(II)]

The title compound, [Cu₂(SO₄)₂(C₁₀H₈N₂)₂(C₂H₆O₂)₂(H₂O)₂]_n, contains two crystallographically unique Cu^II centres, each lying on a twofold axis and having a slightly distorted octahedral environment. One Cu^II centre is coordinated by two bridging 4,4′‐bipyridine (4,4′‐bipy) ligands, two sulfate anions and two aqua ligands. The second is surrounded by two 4,4′‐bipy N atoms and four O atoms, two from bridging sulfate anions and two from ethane‐1,2‐diol ligands. The sulfate anion bridges adjacent Cu^II centres, leading to the formation of linear ...Cu1–Cu2–Cu1–Cu2... chains. Adjacent chains are further bridged by 4,4′‐bipy ligands, which are also located on the twofold axis, resulting in a two‐dimensional layered polymer. In the crystal structure, extensive O—H...O hydrogen‐bonding interactions between water molecules, ethane‐1,2‐diol molecules and sulfate anions lead to the formation of a three‐dimensional supramolecular network structure.     

A one‐dimensional coordination polymer based on Cd2O2 clusters: poly[aqua(μ3‐4,4′‐sulfonyldibenzoato)(3,4,7,8‐tetramethyl‐1,10‐phenanthroline‐κ2N,N′)cadmium(II)]

In the title mixed‐ligand metal–organic polymeric complex [Cd(C₁₄H₈O₆S)(C₁₆H₁₆N₂)(H₂O)]_n, the asymmetric unit contains a crystallographically unique Cd^II atom, one doubly deprotonated 4,4′‐sulfonyldibenzoic acid ligand (H₂SDBA), one 3,4,7,8‐tetramethyl‐1,10‐phenanthroline (TMPHEN) molecule and one water molecule. Each Cd^II centre is coordinated by two N atoms from the chelating TMPHEN ligand, three O atoms from monodentate carboxylate groups of three different SDBA²⁻ ligands and one O atom from a coordinated water molecule, giving a distorted CdN₂O₄ octahedral geometry. Single‐crystal X‐ray diffraction analysis reveals that the compound is a one‐dimensional double‐chain polymer containing 28‐membered rings based on Cd₂O₂ clusters, with a Cd...Cd separation of 3.6889 (4) Å. These chains are linked by O—H...O and C—H...O hydrogen bonds to form a three‐dimensional supramolecular framework. The framework is reinforced by π–π and C—O...π interactions.     

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.     

Di‐μ‐acesulfamato‐κ3N,O:O;κ3O:N,O‐bis[(acesulfamato‐κ2N,O)bis(3‐methylpyridine)cadmium(II)]

In the structure of the title compound, [Cd₂(C₄H₄NO₄S)₂(C₆H₇N)₂], the dinuclear Cd^II complex is located on a twofold axis with two Cd²⁺ ions bridged by two oxide O atoms. Each Cd²⁺ ion is additionally coordinated in an equatorial plane by two N and three O atoms of the acesulfamate ligands and axially by two N atoms of the 3‐methylpyridine ligands, resulting in a distorted pentagonal bipyramidal coordination. We present here an example of a supramolecular assembly based on hydrogen bonds in a mixed‐ligand metal complex; intermolecular C—H...O hydrogen bonds give rise to R₄⁴(40) rings, which lead to one‐dimensional chains.     

Poly[[(μ2‐biphenyl‐2,4′‐dicarboxylato)[μ2‐1,4‐bis(imidazol‐1‐ylmethyl)benzene]cadmium(II)] 0.15‐hydrate]

The asymmetric unit of the title two‐dimensional coordination polymer, {[Cd(C₁₄H₈O₄)(C₁₄H₁₄N₄)]·0.15H₂O}_n, is composed of one Cd^II cation, one biphenyl‐2,4′‐dicarboxylate (bpdc) anion, one 1,4‐bis(imidazol‐1‐ylmethyl)benzene (bix) ligand and 0.15 solvent water molecules. The coordination environment of the Cd^II cation is defined by four carboxylate O atoms from two different bpdc anions in a chelating mode and two N atoms from two distinct bix ligands, constructing a distorted trigonal prism polyhedron. Two inversion‐related Cd^II cations are bridged together by two positionally disordered bpdc anions, forming a 22‐membered ring with a Cd...Cd distance of 9.1966 (9) Å. These rings are then further linked by two bix ligands, extending into a two‐dimensional layer along (102) with 6³ topology.     

Dipotassium di‐μ‐iso­thio­cyanato‐κ4N:S‐bis­[(N‐salicyl­idene‐dl‐valinato‐κ3O,N,O′)­cuprate(II)]

The title compound, K₂[Cu₂(NCS)₂(C₁₂H₁₃NO₃)₂], consists of two K⁺ cations and (N‐salicyl­idene‐d ‐valinato)­cop­per(II) and (N‐salicyl­idene‐l ‐valinato)cop­per(II) coordination units con­nected through three‐atom thio­cyanate (μ‐NCS) bridges into a centrosymmetric dianion. The Cu^II atom adopts a square‐pyramidal coordination, with three donor atoms of the tridentate Schiff base and one N atom of the bridging ligand (μ‐NCS) in the basal plane. The axial position is occupied by the thio­cyanate S atom of a symmetry‐related ligand at an apical distance of 2.9332 (10) Å. Coulombic interactions between six‐coordinated K⁺ ions and the heteroatoms of neighbouring dimeric anions leads to the formation of one‐dimensional chains of mol­ecules parallel to [010]. The superposition of the normals of the pyramidal base planes in a direction close to [001] indicates possible π–π interactions between neighbouring units.     

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.     

μ‐4,4′‐Bipyridine‐κ2N:N′‐bis[triaqua(4,4′‐bipyridine‐κN)cadmium(II)] bis(3‐aminobenzoate) bis(perchlorate) dihydrate: a novel supramolecular system constructed by π–π and hydrogen‐bonding interactions

The title dicadmium compound, [Cd₂(C₁₀H₈N₂)₅(H₂O)₆](C₇H₆NO₂)₂(ClO₄)₂·2H₂O, is located around an inversion centre. Each Cd^II centre is coordinated by three N atoms from three different 4,4′‐bipyridine ligands and three O atoms from three coordinating water molecules in a distorted octahedral coordination environment. In the dicadmium cation unit, one 4,4′‐bipyridine (4,4′‐bipy) molecule acts as a bidentate bridging ligand between two Cd metal ions, while the other four 4,4′‐bipy molecules act only as monodentate terminal ligands, resulting in a rare `H‐type' [Cd₂(C₁₀H₈N₂)₅(H₂O)₆] host unit. These host units are connected to each other viaπ–π stacking interactions, giving rise to a three‐dimensional supramolecular grid network with large cavities. The 3‐aminobenzoate anions, perchlorate anions and water molecules are encapsulated in the cavities by numerous hydrogen‐bonding interactions. To the best of our knowledge, this is the first example of a coordination compound based on both 4,4′‐bipyridine ligands together with discrete 3‐aminobenzoate anions.     

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.     

catena‐Poly­[[bis­(thio­cyanato‐κN)cadmium(II)]‐di‐μ‐thio­urea‐κ4S:S]

The Cd^II ion in the title complex, [Cd(SCN)₂{SC(NH₂)₂}₂]_∞, is situated at a centre of symmetry, and is bound to two N atoms belonging to thio­cyanate groups and to four S atoms of bridging thio­urea ligands. The structure consists of infinite chains of slightly distorted edge‐shared Cd‐centred octahedra. The bridging S atoms of two thio­urea ligands comprise the common edge. Some thermal properties are described.     

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.     

catena‐Poly­[[chloro(1,10‐phenanthroline‐κ2N,N′)copper(II)]‐μ‐imidazolato‐κ2N:N′]

In the polymeric title compound, [Cu(im)Cl(phen)]_n, where im is the imidazolate anion (C₃H₃N₂) and phen is 1,10‐phenanthroline (C₁₂H₈N₂), each Cu^II ion is five‐coordinated by four basal N atoms (two from two different im anions and two from one phen ligand) and one axial Cl atom, in a distorted square‐pyramidal coordination geometry. Moreover, each im anion bridges two identical {CuCl(phen)}⁺ cations through its two N atoms, resulting in a one‐dimensional zigzag chain along the crystallographic a axis. In addition, pairs of adjacent chains are staggered by π–π interactions, generating a two‐dimensional layer, and neighbouring layers are further linked by two different kinds of C—H⋯Cl interactions, producing a three‐dimensional network.     

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[bis­[(2,2‐bi­pyridine‐κ2N,N′)­copper(II)]‐μ4‐1,2,4,5‐benzene­tetra­carboxyl­ato‐κ4O1:O2:O3:O4]

In the title complex, [Cu₂(C₁₀H₂O₈)(C₁₀H₈N₂)₂]_n, the Cu^II cation has a four‐coordinated environment, completed by two carboxyl O atoms belonging to two 1,2,4,5‐benzene­tetra­carboxyl­ate anions (TCB⁴⁻) and two N atoms from one 2,2′‐bi­pyridine (2,2′‐bipy) ligand, forming a distorted square‐planar geometry. The [Cu(2,2′‐bipy)]²⁺ moieties are bridged by TCB⁴⁻ anions, which lie about inversion centres, forming an infinite one‐dimensional coordination polymer with a double‐chain structure along the a axis. A two‐dimensional network structure is formed via a face‐to‐face π–π interaction between the 2,2′‐bipy rings belonging to two adjacent double chains, at a distance of approximately 3.56 Å.     

catena‐Poly[[[cis‐aqua­bis(4‐carboxy­cyclo­hexane‐1‐carboxyl­ato‐κ2O,O′)cadmium(II)]‐μ‐4,4′‐bipyridine‐κ2N:N] monohydrate]

The title complex, {[Cd(C₈H₁₁O₄)₂(C₁₀H₈N₂)(H₂O)]·H₂O}_n, consists of linear chains formed through 4,4′‐bipyridine ligands linking seven‐coordinated Cd^II ions. Each Cd^II ion is in a distorted penta­gonal–bipyramidal environment, coordinated by one water ligand, two 4‐carboxy­cyclo­hexane‐1‐carboxyl­ate ligands and one bridging 4,4′‐bipyridine ligand to generate linear chains. The water mol­ecules and the Cd atom on one side, and the 4,4′‐bipyridine unit on the other, are bisected by two sets of twofold axes. The carboxylate group of the 4‐carboxy­cyclo­hexane‐1‐carboxyl ligand chelates a Cd^II ion, while the (protonated) carboxyl group forms hydrogen bonds with adjacent chains, resulting in a layered structure. This is the first reported occurrence of a dicarboxycyclo­hexane ligand exhibiting a non‐bridging coordination mode.     

Poly­[[bis(1H‐benz­imidazole‐κN3)cadmium(II)]‐μ‐aqua‐μ‐succinato‐κ2O1:O4]

The title compound, [Cd(C₄H₄O₄)(C₇H₆N₂)₂(H₂O)]_n, is a three‐dimensional polymeric complex. The Cd^II atom is located on an inversion centre and assumes an elongated octahedral coordination geometry, with a long Cd—O distance of 2.5381 (5) Å to the coordinated bridging water molecule. The succinate dianion, located on another inversion centre, bridges adjacent Cd atoms to form succinate‐bridged polymeric chains. The coordinated water mol­ecule is located on a twofold axis and links adjacent succinate‐bridged chains to form a water‐bridged polymeric chain.