A novel helical copper complex: catena‐poly[[[aquacopper(II)]‐μ‐N‐(3‐carboxy‐2‐oxidobenzylidene‐κO2)glycinato‐κ3N,O′:O′] monohydrate]

In the polymeric title compound, {[Cu(C₁₀H₇NO₅)(H₂O)]·H₂O}_n, the Cu atom adopts a square‐based pyramidal coordination involving a N,O,O′‐tridentate glycine dianionic ligand, a water O atom and an apical bridging carboxylate O atom from an adjacent ligand. The title compound also adopts a carboxylate‐bridged chain structure. The molecular chain propagates in a helical fashion along the b axis of the monoclinic unit cell. Neighbouring chains are linked together to form a three‐dimensional network via hydrogen‐bonding interactions between coordinated and uncoordinated water molecules and O atoms of the bridging carboxylate groups.     

μ‐Acetato‐1:2κ2O:O′‐diacetato‐1κ2O,O′;2κO‐bis(di‐2‐pyridylamine)‐1κ2N,N′;2κ2N,N′‐isothiocyanato‐2κN‐dicopper(II)

In the title dinuclear acetate‐bridged complex, [Cu₂(C₂H₃O₂)₃(NCS)(C₁₀H₉N₃)₂], the two Cu atoms are five‐coordinated, with a basal plane consisting of two N atoms of a di‐2‐pyridylamine (dpyam) ligand and two O atoms of two different acetate ligands. The axial positions of these Cu atoms are coordinated to N and O atoms from thio­cyanate and acetate mol­ecules, respectively, leading to a distorted square‐pyramidal geometry with τ values of 0.30 and 0.22. Both Cu^II ions are linked by an acetate group in the equatorial–equatorial positions and have syn–anti bridging configurations. Hydrogen‐bond inter­actions between the amine H atom and the coordinated and uncoordinated O atoms of the acetate anions generate an infinite one‐dimensional chain.     

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[[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‐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.     

Di‐μ‐formato‐1κ2O:2κ2O′‐di‐μ‐pyridin‐2‐olato‐1κO:2κN;1κN:2κO‐bis­[(2‐pyridone‐κO)copper(II)] acetonitrile 1.02‐solvate

In the title compound, [Cu₂(CHO₂)₂(C₅H₄NO)₂(C₅H₅NO)₂]·1.02CH₃CN, the dimeric unit is centrosymmetric, with two bidentate pyridin‐2‐olate and two bidentate formate syn–syn bridges, and two apical 2‐pyridone ligands coordinated through the O atoms. The N atom from the apical 2‐pyridone ligand is a donor of a hydrogen bond to the O atom of the bridging pyridinolate ligand of the same complex. The coordination polyhedron of the Cu atom is a distorted square pyramid.     

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.     

catena‐Poly[[[triaquazinc(II)]‐μ‐2‐nitroterephthalato‐κO1:κ2O4,O4′] monohydrate]

The title complex, {[Zn(C₈H₃NO₆)(H₂O)₃]·H₂O}_n, has a one‐dimensional chain structure. The two carboxylate groups of the dianionic 2‐nitroterephthalate ligand adopt mono‐ and bidentate chelating modes. The Zn atom shows distorted octahedral coordination, bonded to three O atoms from two carboxylate groups and 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 stabilized by inter‐layer hydrogen bonds.     

Poly[[aqua(4,4′‐diazenediyldibenzoato‐κ4O,O′:O′′,O′′′)cadmium(II)]: a twofold interpenetrated three‐dimensional coordination polymer of PtS topology

In the title coordination compound, [Cd(C₁₄H₈N₂O₄)(H₂O)]_n, the Cd^II cation and the coordinated water molecule lie on a twofold axis, whereas the ligand lies on an inversion center. The Cd^II center is five‐coordinated in a distorted square‐pyramidal geometry by four carboxylate O atoms from four different 4,4′‐diazenediyldibenzoate (ddb) anions and one water O atom. The three‐dimensional frameworks thus formed by the bridging ddb anions interpenetrate to generate a three‐dimensional PtS‐type network. Additionally, the coordination water molecule and the carboxylate O atom form a hydrogen‐bonding interaction, stabilizing the three‐dimensional framework structure.     

A novel dinuclear bismuth(III) coordination compound: bis(μ‐pyridine‐2,6‐dicarboxylato)‐κ4O2,N,O6:O6′;κ4O2:O2′,N,O6‐bis[(azido‐κN)(1,10‐phenanthroline‐κ2N,N′)bismuth(III)] tetrahydrate

A novel dinuclear bismuth(III) coordination compound, [Bi₂(C₇H₃NO₄)₂(N₃)₂(C₁₂H₈N₂)₂]·4H₂O, has been synthesized by an ionothermal method and characterized by elemental analysis, energy‐dispersive X‐ray spectroscopy, IR, X‐ray photoelectron spectroscopy and single‐crystal X‐ray diffraction. The molecular structure consists of one centrosymmetric dinuclear neutral fragment and four water molecules. Within the dinuclear fragment, each Bi^III centre is seven‐coordinated by three O atoms and four N atoms. The coordination geometry of each Bi^III atom is distorted pentagonal–bipyramidal (BiO₃N₄), with one azide N atom and one bridging carboxylate O atom located in axial positions. The carboxylate O atoms and water molecules are assembled via O—H...O hydrogen bonds, resulting in the formation of a three‐dimensional supramolecular structure. Two types of π–π stacking interactions are found, with centroid‐to‐centroid distances of 3.461 (4) and 3.641 (4) Å.     

A one‐dimensional coordination polymer with metal–metal inter­actions: catena‐poly­[[tri­aqua­barium(II)]‐μ‐aqua‐κ2O:O‐di‐μ‐thio­salicyl­ato‐κ4O:O]

In the title compound, [Ba(C₇H₅O₂S)₂(H₂O)₄]_n, the Ba^II atom lies on a mirror plane and is nine‐coordinated by four bridging carboxylate O atoms of the thio­salicyl­ate ligands, two bridging water mol­ecules and three terminal water mol­ecules. There is an intramolecular S—H⋯O hydrogen bond between the S and O atoms in the thio­salicyl­ate ligand. A one‐dimensional coordination polymer is formed via weak metal–metal interactions along polymeric zigzag chains.     

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[[[(di‐2‐pyridylamine‐κ2N2,N2′)copper(II)]‐μ‐benzene‐1,3‐dicarboxylato‐κ3O1,O1′:O3] monohydrate], a zigzag coordination polymer with strong π–π interactions

The novel title coordination polymer, {[Cu(C₈H₄O₄)(C₁₀H₉N₃)]·H₂O}_n, synthesized by the slow‐diffusion method, takes the form of one‐dimensional zigzag chains built up of Cu^II cations linked by benzene‐1,3‐dicarboxylate (ipht) anions. An exceptional characteristic of this structure is that it belongs to a small group of metal–organic polymers where ipht is coordinated as a bridging tridentate ligand with monodentate and chelate coordination of individual carboxylate groups. The Cu^II cation has a highly distorted square‐pyramidal geometry formed by three O atoms from two ipht anions and two N atoms from a di‐2‐pyridylamine (dipya) ligand. The zigzag chains, which run along the b axis, further construct a three‐dimensional metal–organic framework via strong face‐to‐face π–π interactions and hydrogen bonds. A solvent water molecule is linked to the different carboxylate groups via hydrogen bonds. Thermogravimetric and differential scanning calorimetric analyses confirm the strong hydrogen bonding.     

(μ‐C‐meso‐5,5,7,12,12,14‐Hexa­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐N‐acetato‐1κ5N,N′,N′′,N′′′,O:2κO′)­tetra­chloro‐1κCl,2κ3Cl‐cobalt(III)­zinc(II)

The crystal structure of the title compound, [CoCl(C₁₈H₃₇N₄O₂){ZnCl₃}], has been determined by X‐ray diffraction.C‐meso‐5,5,7,12,12,14‐Hexa­methyl‐1,4,8,11‐tetra­aza­cyclotetradecane‐N‐acetate acts as a bridging ligand to coodinate with Co^III and Zn^II ions. The Co^III ion is six‐coordinate in a nearly octahedral environment provided by one Cl atom, four N atoms of the bridging ligand, and one O atom. The Zn^II ion is four‐coordinate in a distorted tetrahedral environment completed by three Cl atoms and an O atom of the bridging ligand.     

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.     

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.     

(μ‐2,11‐Dithia­[3.3]paracyclo­phane‐κ2S:S′)bis­[(6‐carboxy­pyridine‐2‐carboxylato‐κ2N,O6)silver(I)]: a mixed‐ligand silver‐based dinuclear compound

In the title complex, [Ag₂(C₇H₄NO₄)₂(C₁₆H₁₆S₂)], each Ag^I atom is trigonally coordinated by one S atom of a 2,11‐dithia­[3.3]paracyclo­phane (dtpcp) ligand, and by one N and one O atom of a 6‐carboxy­pyridine‐2‐carboxylate ligand. Dtpcp acts as a bidentate ligand, bridging two inversion‐related Ag^I atoms to give a dinuclear silver(I) compound. The dinuclear moieties are inter­connected via O—H·O hydrogen bonds to form a two‐dimensional zigzag sheet. Two such sheets are inter­woven viaπ–π inter­actions between pyridine rings, affording an inter­woven bilayer network.     

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.     

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[[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.