Poly[aqua‐μ3‐2,2‐dimethyl­malonato‐zinc(II)]

The title complex, [Zn(C₅H₆O₄)(H₂O)]_n, has a two‐dimensional layer structure. The Zn atoms, in a geometry that is closer to trigonal bipyramidal than square pyramidal, are coordinated by two O atoms of a bidentate dimethyl­malonate ligand, two O atoms of monodentate dimethylmalonate ligands and one O atom from the aqua ligand. The crystal structure is characterized by the intra­layer motif of a hydrogen‐bonded network. Neighboring layers are linked together to build up a three‐dimensional network via van der Waals forces.     

Poly[μ‐aqua‐diaqua‐μ4‐malonato‐μ3‐malonato‐barium(II)nickel(II)]

The title complex, [BaNi(C₃H₂O₄)₂(H₂O)₃]_n, is polymeric, with two non‐equivalent malonate dianions bridging one Ni atom and five different Ba atoms. The Ni atoms have a distorted octahedral (NiO₆) environment, and are coordinated by four malonate O atoms in a planar arrangement and two water molecules in axial positions. The Ba atom may be described as a BaO₉ polyhedron in a monocapped square‐antiprismatic environment, which involves two water molecules and seven O atoms from different malonate ligands. The three‐dimensional structure is further maintained and stabilized by hydrogen bonds.     

Poly[tetraaquadi‐μ4‐malonato‐barium(II)zinc(II)]

The title complex, [BaZn(C₃H₂O₄)₂(H₂O)₄]_n, is polymeric, due to the connectivity brought about by each malonate dianion bonding to two different Zn^II cations and two different Ba^II cations. The Ba^II cations, on crystallographic twofold axes, have slightly distorted square‐anti­prismic coordination, with Ba—O distances ranging from 2.795 (2) to 2.848 (2) Å. The Zn^II cations, which lie on crystallographic centres of symmetry, have distorted octa­hedral coordination, with Zn—O bonds in the range 2.0364 (19)–2.3248 (18) Å. The water mol­ecules participate in extensive O—H⋯O hydrogen bonding. The structure comprises alternating layers along [100], with one type containing Zn^II cations and malonate dianions, while the other is primarily composed of Ba^II cations and water mol­ecules.     

Poly[[aqua‐μ3‐2,2‐dimethylmalonato‐copper(II)] monohydrate] and poly[aqua‐μ3‐2,2‐dimethylmalonato‐copper(II)]

The coordination mode of the dimethylmalonate ligand in the two title Cu^II complexes, {[Cu(C₅H₃O₄)(H₂O)]·H₂O}_n, (I), and [Cu(C₅H₃O₄)(H₂O)]_n, (II), is the same, with chelated six‐membered, bis‐monodentate and bridging bonding modes. However, the coordination environment of the Cu^II atoms, the connectivity of their metal–organic frameworks and their hydrogen‐bonding interactions are different. Complex (I) has a perfect square‐pyramidal Cu^II environment with the aqua ligand in the apical position, and only one type of square grid consisting of Cu^II atoms linked via carboxylate bridges to three dimethylmalonate ligands, with weak hydrogen‐bond interactions within and between its two‐dimensional layers. Complex (II) has a coordination geometry that is closer to square pyramidal than trigonal bipyramidal for its Cu^II atoms with the aqua ligand now in the basal plane. Its two‐dimensional layer structure comprises two alternating grids, which involve two and four different dimethylmalonate anions, respectively. There are strong hydrogen bonds only within its layers.     

Poly[tetra‐μ‐aqua‐hexa­aquadi‐μ3‐malon­ato‐dinitratodibarium(II)nickel(II)]

The title complex, [Ba₂Ni(C₃H₂O₄)₂(NO₃)₂(H₂O)₁₀]_n, has a two‐dimensional layer structure. The Ni atom lies on a crystallographic centre of symmetry in an octa­hedral NiO₆ environment, and is coordinated by four malonate O atoms in a planar arrangement and by two water mol­ecules in axial positions. The coordination of the unique Ba atom involves two nitrate O atoms, five water mol­ecules and three malonate O atoms.     

Poly[μ2‐4‐aminobenzoato‐aqua‐μ2‐nitrato‐zinc]

In the title compound, [Zn(C₇H₆NO₂)(NO₃)(H₂O)]_n, the Zn atom is coordinated by two nitrate ions, one aqua molecule and two 4‐aminobenzoate ions in a distorted octahedral geometry. The structure of the compound exhibits a two‐dimensional layer, which is formed by the interconnection of [Zn(C₇H₆NO₂)(H₂O)]_n chains viaμ₂‐nitrate bridges or by the interconnection of [Zn(NO₃)(H₂O)]_n chains viaμ₂‐4‐aminobenzoate bridges.     

Poly[[di‐μ3‐acetato‐di‐μ2‐aqua‐diaqua‐di‐μ3‐hydroxo‐tricopper(II)] naphthalene‐1,5‐disulfonate]

The crystal structure of the title complex, {[Cu₃(C₂H₃O₂)₂(OH)₂(H₂O)₄](C₁₀H₆O₆S₂)}_n, is built of infinite polymeric cationic {[Cu₃(C₂H₃O₂)₂(H₂O)₄(OH)₂]²⁺}_n chains stretching along the a axis, with naphthalene‐1,5‐disulfonate (1,5‐nds) anions in between. One independent Cu^II cation and the 1,5‐nds anion occupy special positions on crystallographic inversion centres. Each Cu^II cation has an octa­hedral coordination environment formed by two carboxyl O atoms, two hydroxo O atoms and two water mol­ecules. The carboxyl­ate and hydroxo groups perform a bridging function, linking adjacent Cu atoms in the chain, with a shortest Cu⋯Cu distance of 2.990 (3) Å. The chains are further linked into a three‐dimensional supra­molecular framework via hydrogen‐bonding inter­actions involving the sulfonate groups of the 1,5‐­nds dianions.     

Poly[tetra­aqua­di‐μ3‐malonato‐calcium(II)­zinc(II)]

The title complex, [CaZn(C₃H₂O₄)₂(H₂O)₄]_n, is a two‐dimensional polymer and consists of CaO₈ and ZnO₆ polyhedra linked together by malonate ligands. The Ca^II cation, lying on a twofold axis, is coordinated by two water mol­ecules and six malonate O atoms. The Zn^II cation, which lies on an inversion center in an octa­hedral environment, is coordinated by four malonate O atoms in an equatorial arrangement and two water mol­ecules in axial positions. The Zn—O and Ca—O bond lengths are in the ranges 2.0445 (12)–2.1346 (16) and 2.3831 (13)–2.6630 (13) Å, respectively. The structure comprises alternating layers along the [101] plane, the shortest Zn⋯Zn distance being 6.8172 (8) Å. The whole three‐dimensional structure is maintained and stabilized by the presence of hydrogen bonds.     

Poly[[di‐μ‐aqua‐tetraaquadi‐μ‐hydroxido‐bis(μ3‐3‐nitrophthalato)tricopper(II)] dihydrate]

The novel title complex, {[Cu₃(C₈H₃NO₆)₂(OH)₂(H₂O)₆]·2H₂O}_n, has a one‐dimensional polymeric double chain structure where the three Cu atoms are linked by μ₂‐OH and μ₂‐H₂O groups, and these trinuclear centres are bridged by two 3‐nitrophthalate ligands. The asymmetric unit contains one and a half crystallographically independent Cu atoms (one lying on a centre of inversion), both coordinated by six O atoms and exhibiting distorted octahedral coordination geometries, but with different coordination environments. Each 3‐nitrophthalate ligand connects to three Cu atoms through two O atoms of one carboxylate group and one O atom of the nitro group. The remaining carboxylate group is free and is involved in intrachain hydrogen bonds, reinforcing the chain linkage.     

Poly[hexaaquabis(μ4‐4‐carboxybenzenesulfonato)bis(μ3‐4‐carboxybenzenesulfonato)calcium(II)dipotassium(I)]

This study presents the coordination modes and crystal organization of a calcium–potassium coordination polymer, poly[hexaaquabis(μ₄‐4‐carboxybenzenesulfonato‐κ⁴O¹:O^1′:O^1′′:O⁴)bis(μ₃‐4‐carboxybenzenesulfonato‐κ²O¹:O^1′)calcium(II)dipotassium(I)], [CaK₂(C₇H₅O₅S)₄(H₂O)₆]_n, displaying a novel two‐dimensional framework. The potassium ion is seven‐coordinated by four sulfonate and one carboxyl O atom located on five different acid ligands, two of which are unique, and by two symmetry‐independent water O atoms. A pair of close potassium ions share two inversion‐related sulfonate O‐atom sites to form a dimeric K₂O₁₂ unit, which is extended into a one‐dimensional array along the a‐axis direction. The six‐coordinate Ca²⁺ ion occupies a special position () at (0, , ) and is surrounded by four sulfonate O atoms from two inversion‐related pairs of unique acid monoanions and by two O atoms from aqua ligands. The compound displays a layered structure, with K₂O₁₂ and CaO₆ polyhedra in the layers and aromatic linkers between the layers. The three‐dimensional scaffold is open, with nano‐sized channels along the c axis.     

Poly[diaquabis(μ3‐2,2‐dimethylpropanedioato)calcium(II)copper(II)]

The title complex, [CaCu(C₅H₆O₄)₂(H₂O)₂]_n, is the first heterobimetallic complex based on a substituted malonate dianion. The Cu^II cation and two independent 2,2‐dimethylmalonate (or 2,2‐dimethylpropanedioate) dianions build up a robust dianionic [Cu(C₅H₆O₄)₂]²⁻ complex, which acts as a building block to coordinate to four Ca²⁺ cations. Each Cu^II centre is in a four‐coordinate square plane of dimethylmalonate O atoms, while each Ca^II atom is in an eight‐coordinate distorted bicapped trigonal–prismatic environment of six O atoms from four different dimethylmalonate groups and two water molecules. This arrangement creates a two‐dimensional layer connectivity of the structure. The dianionic [Cu(C₅H₆O₄)₂]²⁻ units are involved in different intermolecular hydrogen‐bonding interactions with water molecules via the formation of hydrogen‐bonded rings of graph sets R₁²(8) and R(6) within this layer. The crystal was nonmerohedrally twinned by rotation about [011] with a major twin volume fraction of 0.513 (3).     

Poly[diaqua[μ4‐4‐(isonicotinamido)phthalato]nickel(II)] displaying an sra topology

In the title compound, [Ni(C₁₄H₈N₂O₅)(H₂O)₂]_n, the Ni^II cation is six‐coordinate with a slightly distorted octahedral coordination geometry and the 4‐(isonicotinamido)phthalate ligand links the Ni^II centres into a three‐dimensional structure with sra topology. The structure is also stabilized by N—H...O hydrogen bonding between the uncoordinated amide groups of the ligand and extensive O—H...O hydrogen bonding between the two coordinated water molecules. The magnetic and thermal stability properties of the title compound are also discussed.     

Poly[[μ‐aqua‐bis­(μ‐2,4‐dichloro­phen­oxy­acetato)barium(II)] monohydrate]

In the title coordination polymer, {[Ba(C₈H₅Cl₂O₃)₂(H₂O)]·H₂O}_n, each Ba^II atom is nine‐coordinated by six carboxyl­ate O atoms and one ether O atom from five symmetry‐related 2,4‐dichloro­phenoxy­acetate ligands, and by two O atoms from water mol­ecules, thus defining a distorted tricapped trigonal prism. The Ba^II ions are bridged by bidentate water mol­ecules and by tridentate and tetra­dentate 2,4‐dichloro­phenoxy­acetate groups, leading to a two‐dimensional layer structure. The crystal structure is further stabilized by hydrogen‐bonding inter­actions within each layer.     

Poly[bis(4‐chloropyridinium) tetra‐μ2‐chlorido‐tetrachloridotrimercurate(II)]

The structure of the title compound, {(C₅H₅ClN)₂[Hg₃Cl₈]}_n, consists of 4‐chloropyridinium cations and one‐dimensional [Hg₃Cl₈]²⁻ anion chains. There are two coordination environments for Hg^II in the inorganic chain. The first is a distorted tetrahedral geometry made up of an HgCl₂ unit with two Cl⁻ anion bridges, while the second is an octahedral coordination geometry consisting of an HgCl₂ unit and four chloride‐anion bridges. This gives rise to a novel three‐layer centrosymmetric polymer. Finally, the three‐dimensional network comes about through the many C—H...Cl and N—H...Cl hydrogen bonds that link the organic and inorganic layers.     

Poly[μ7‐sulfanediyldiacetato‐disilver(I)]

In the title coordination polymer, [Ag₂(C₄H₄O₄S)], each Ag^I cation is four‐coordinated by three of the four carboxylate O atoms and the S atom from symmetry‐related sulfanediyldiacetate ligands, thus defining a distorted tetrahedral geometry at the metal centre. The Ag^I cations are bridged by sulfanediyldiacetate groups, leading to a two‐dimensional layer structure. These layers are interconnected via Ag—S bonds to form a three‐dimensional coordination polymer network overall.     

Poly[bis[aquaneodymium(III)]‐μ2‐oxalato‐di‐μ4‐succinato]

In the title compound, [Nd₂(C₄H₄O₄)₂(C₂O₄)(H₂O)₂]_n, the flexible succinate anion assumes the gauche conformation and bridges the nine‐coordinate Nd atoms to generate two‐dimensional layers parallel to (010). The coordination polymer layers are linked into a three‐dimensional framework by the rigid oxalate ligands. The oxalate ions are located on a center of inversion.     

Poly[di‐μ‐aqua‐[μ6‐N‐(4‐bromophenylsulfonyl)dithiocarbimato]dipotassium] and poly[di‐μ‐aqua‐[μ4‐N‐(4‐iodophenylsulfonyl)dithiocarbimato]dipotassium]

The rigid organic linkers N‐(4‐bromophenylsulfonyl)dithiocarbimate(2−) and N‐(4‐iodophenylsulfonyl)dithiocarbimate(2−) crystallize with two potassium cations and two water molecules in their asymmetric units, forming the title coordination polymers, [K₂(C₇H₄BrNO₂S₃)(H₂O)₂]_n and [K₂(C₇H₄INO₂S₃)(H₂O)₂]_n. The anions and the water molecules link the potassium cations into broad two‐dimensional networks, which are further linked by K...halide interactions.     

Poly[tetra­aquadi‐μ3‐malonato‐cobalt(II)­calcium(II)]

The structure of the polymeric title compound, [CaCo(C₃H₂O₄)₂(H₂O)₄]_n, consists of CaO₈ and CoO₆ polyhedra linked together by malonate groups. The Co atom lies on a centre of symmetry in an octa­hedral arrangement, and is coordinated by four malonate O atoms in a planar arrangement and two water mol­ecules in a trans conformation. The geometry around the Ca atom, which lies on a twofold axis, may be described as a distorted square anti­prism, which involves two water mol­ecules and six malonate O atoms. The Co—O and Ca—O bond lengths are in the ranges 2.0711 (12)–2.1004 (14) and 2.3775 (12)–2.6329 (12) Å, respectively.     

μ‐Acetato‐μ‐aqua‐μ‐hydroxido‐bis[(1,10‐phenanthroline)copper(II)] dinitrate monohydrate

The triply bridged title dinuclear copper(II) compound, [Cu₂(C₂H₃O₂)(OH)(C₁₂H₈N₂)₂(H₂O)](NO₃)₂·H₂O, (I), consists of a [Cu₂(μ₂‐CH₃COO)(μ₂‐OH)(phen)₂(μ₂‐OH₂)]²⁺ cation (phen is 1,10‐phenanthroline), two uncoordinated nitrate anions and one water molecule. The title cation contains a distorted square‐pyramidal arrangement around each metal centre with a CuN₂O₃ chromophore. In the dinuclear unit, both Cu^II ions are linked through a hydroxide bridge and a triatomic bridging carboxylate group, and at the axial positions through a water molecule. The phenanthroline groups in neighbouring dinuclear units interdigitate along the [010] direction, generating several π–π contacts which give rise to planar arrays parallel to (001). These are in turn connected by hydrogen bonds involving the aqua and hydroxide groups as donors with the nitrate anions as acceptors. Comparisons are made with isostructural compounds having similar cationic units but different counter‐ions; the role of hydrogen bonding in the overall three‐dimensional structure and its ultimate effect on the cell dimensions are discussed.     

catena‐Poly[tris(μ3‐acetylacetonato)nickelate(II)sodium(I)]

The title complex, [NaNi(C₅H₇O₂)₃]_n, contains an anionic tris(acetylacetonato)nickelate(II) unit, [Ni(acac)₃]⁻ (acac is acetylacetonate), with a highly regular octahedral coordination geometry. The Ni^II cation lies on a Wyckoff a site, resulting in D₃ symmetry of the anion. Charge balance is provided by sodium cations, which occupy Wyckoff type b sites. Each sodium cation is surrounded by two [Ni(acac)₃]⁻ anions, each of which is connected to the alkali metal through three O atoms, in a fac configuration. This arrangement leads to the formation of linear [Na{Ni(acac)₃}]_n chains along the c axis. The Ni...Na distance is 2.9211 (10) Å. The title complex is one of the few examples of heterometallic systems based on alkali and transition metal cations bridged by acetylacetonate ligands.