catena‐Poly[[bis(nicotinamide‐κN1)copper(I)]‐μ‐thiocyanato‐κ2N:S]

The Cu^I cations in the title compound, [Cu(NCS)(C₆H₆N₂O)₂]_n, are coordinated by N atoms from each of two mirror‐related nicotin­amide ligands, as well as by one N atom of one thio­cyanate ligand and one S atom of a symmetry‐related thio­cyanate ligand, within a slightly distorted tetrahedron. The Cu^I cations and the thio­cyanate anions are located on a crystallographic mirror plane and the nicotin­amide ligands occupy general positions. The Cu^I cations are connected by the thio­cyanate anions to form chains in the direction of the crystallographic a axis. These chains are connected by hydrogen bonds between the amide H atoms and the O atoms of adjacent nicotin­amide ligands, to give a three‐dimensional structure.     

Poly[diaqua(μ‐4,4′‐bipyridine‐κ2N:N′)bis(μ‐cyanido‐κ2C:N)bis(cyanido‐κC)nickel(II)copper(II)]: a metal–organic cyanide‐bridged framework

The structure of the title compound, [NiCu(CN)₄(C₁₀H₈N₂)(H₂O)₂]_n or [{Cu(H₂O)₂}(μ‐C₁₀H₈N₂)(μ‐CN)₂{Ni(CN)₂}]_n, was shown to be a metal–organic cyanide‐bridged framework, composed essentially of –Cu–4,4′‐bpy–Cu–4,4′‐bpy–Cu– chains (4,4′‐bpy is 4,4′‐bipyridine) linked by [Ni(CN)₄]²⁻ anions. Both metal atoms sit on special positions; the Cu^II atom occupies an inversion center, while the Ni^II atom of the cyanometallate sits on a twofold axis. The 4,4′‐bpy ligand is also situated about a center of symmetry, located at the center of the bridging C—C bond. The scientific impact of this structure lies in the unique manner in which the framework is built up. The arrangement of the –Cu–4,4′‐bpy–Cu–4,4′‐bpy–Cu– chains, which are mutually perpendicular and non‐intersecting, creates large channels running parallel to the c axis. Within these channels, the [Ni(CN)₄]²⁻ anions coordinate to successive Cu^II atoms, forming zigzag –Cu—N[triple‐bond]C—Ni—C[triple‐bond]N—Cu– chains. In this manner, a three‐dimensional framework structure is constructed. To the authors' knowledge, this arrangement has not been observed in any of the many copper(II)–4,4′‐bipyridine framework complexes synthesized to date. The coordination environment of the Cu^II atom is completed by two water molecules. The framework is further strengthened by O—H...N hydrogen bonds involving the water molecules and the symmetry‐equivalent nonbridging cyanide N atoms.     

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.     

A novel three‐dimensional heterometallic coordination polymer: poly[[diaquadi‐μ3‐chlorido‐μ2‐chlorido‐tri‐μ3‐nicotinato‐tricopper(I)gadolinium(III)] hemihydrate]

In the title polymeric heterometallic compound, {[Cu₃Gd(C₆H₄NO₂)₃Cl₃(H₂O)₂]·0.5H₂O}_n, comprising copper(I) and gadolinium(III) cations bridged by nicotinate (nic) ligands and chloride anions, the Gd^III centers display a bicapped trigonal prismatic geometry, defined by six carboxylate O atoms and two water molecules. For copper(I), one Cu center is three‐coordinated by three chloride ions and displays a trigonal–planar geometry; the other two Cu centers are four‐coordinated and display a very distorted tetrahedral geometry. The chloride anions act in μ₂‐ and μ₃‐bridging modes, linking the Cu^I ions into an infinite chain. The nic ligand exhibits a tridentate coordination mode, with the carboxylate O atoms linking to two Gd^III ions and the N atom linking to one Cu^I ion. Thus, a novel three‐dimensional heterometallic coordination polymer is constructed from Gd–carboxylate subunits and Cu—Cl chains. In addition, intra‐ and intermolecular O—H...O and O—H...Cl hydrogen bonds are also observed within the three‐dimensional structure. Topologically, the framework represents an unusual 3,6‐connected (4.8²)₃(4¹⁰.6⁵) net.     

Poly[aqua(μ2‐benzene‐1,4‐dicarboxylato)(μ2‐4,4′‐bipyridine N,N′‐dioxide)cadmium(II)], a threefold interpenetrating diamond net

In the title compound, [Cd(C₈H₄O₄)(C₁₀H₈N₂O₂)(H₂O)]_n, (I), each Cd^II atom is seven‐coordinated in a distorted monocapped trigonal prismatic coordination geometry, surrounded by four carboxylate O atoms from two different benzene‐1,4‐dicarboxylate (1,4‐bdc) anions, two O atoms from two distinct 4,4′‐bipyridine N,N′‐dioxide (bpdo) ligands and one water O atom. The Cd^II atom and the water O atom are on a twofold rotation axis. The bpdo and 1,4‐bdc ligands are on centers of inversion. Each crystallographically unique Cd^II center is bridged by the 1,4‐bdc dianions and bpdo ligands to give a three‐dimensional diamond framework containing large adamantanoid cages. Three identical such nets are interlocked with each other, thus directly leading to the formation of a threefold interpenetrated three‐dimensional diamond architecture. To the best of our knowledge, (I) is the first example of a threefold interpenetrating diamond net based on both bpdo and carboxylate ligands. There are strong linear O—H...O hydrogen bonds between the water molecules and carboxylate O atoms within different diamond nets. Each diamond net is hydrogen bonded to its two neighbors through these hydrogen bonds, which further consolidates the threefold interpenetrating diamond framework.     

Poly[[aqua­copper(II)]‐μ‐adamantane‐1,3‐diacetato]

In the title compound, [Cu(C₁₄H₁₈O₄)(H₂O)]_n, each Cu^II atom bonds to four O atoms of four adamantanediacetate (ada) ligands in equatorial positions and an O atom from a water mol­ecule in the apical position. Two adjacent Cu^II atoms form a paddle‐wheel unit with four ada ligands. The distance between the two Cu atoms is 2.5977 (3) Å. A crystallographic inversion center is located at the center of the Cu–Cu core. Each Cu₂(ada)₄ paddle‐wheel further bonds to four adjacent identical paddle‐wheel units, generating a two‐dimensional layered structure of Cu(ada)(H₂O) with a 4⁴ topology.     

Di‐μ‐chlorido‐bis({2‐[1‐(2‐pyridylethylimino)ethyl]pyrrolato‐κ3N,N′,N′′}copper(II))

The title compound, [Cu₂(C₁₃H₁₄N₃)₂Cl₂], is a neutral dimeric copper(II) complex. The two Cu^II atoms are asymmetrically bridged by two chloride ions. Each Cu^II atom is also bound to the three N atoms of a deprotonated tridentate Schiff base ligand, giving a distorted square‐pyramidal N₃Cl₂ coordination environment overall. The dinuclear complex lies across an inversion centre in the space group P. This work demonstrates the effect of ligand flexibility and steric constraints on the structures of copper(II) complexes.     

catena‐Poly[hexaaquamagnesium(II) [bis(μ3‐5‐nitro‐2‐oxidoisophthalato)dicopper(II)] dihydrate]

In the centrosymmetric dinuclear anions of the title bimetallic complex, {[Mg(H₂O)₆][Cu₂(C₈H₂NO₇)₂]·2H₂O}_n, each Cu^II ion is strongly coordinated by four O atoms in a distorted square‐planar geometry. Two of these O atoms belong to phenolate groups and the other two to carboxylate groups from 5‐nitro‐2‐oxidoisophthalate (L1) trianions, derived from 5‐nitrobenzene‐1,2,3‐tricarboxylic acid (O₂N–H₃L). The phenolate O atoms bridge the two Cu^II ions in the anion. In addition, each Cu^II cation interacts weakly with a symmetry‐related carboxylate O atom of an adjacent L1 ligand, giving a square‐pyramidal coordination geometry. The copper residue forms a ladder‐like linear coordination polymer via L1 ligands. The [Mg(H₂O)₆]²⁺ cations sit on centres of inversion. The polymeric anions, cations and free water molecules are self‐assembled into a three‐dimensional supramolecular network via O—H...O hydrogen bonds.     

Tetra‐μ2‐acetato‐diacetatodi‐μ3‐hydroxido‐tetrakis[piperidinecopper(II)] dihydrate

The title complex, [Cu₄(C₂H₃O₂)₆(OH)₂(C₅H₁₁N)₄]·2H₂O, possesses an unusual inversion‐symmetric tetranuclear copper framework, with each Cu^II atom displaying a square‐pyramidal geometry and one additional long Cu...O contact. The four piperidine ligands are terminal, one at each Cu^II atom, and the two hydroxide ligands are triply bridging. The six acetate ligands exhibit two distinct coordination modes, namely as two monodentate acetates and four bridging acetates that bridge the two inequivalent copper centres. The noncoordinating acetate O atom is involved in intramolecular hydrogen bonding with H atoms from the hydroxide and one piperidine ligand. In addition, extensive intermolecular hydrogen bonding involving the solvent water molecules is observed.     

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.     

catena‐Poly[[(1,10‐phenanthroline‐κ2N,N′)copper(II)]‐μ‐(dihydrogen benzene‐1,2,4,5‐tetracarboxylato)‐κ2O1:O4]

In the title compound, [Cu(C₁₀H₄O₈)(C₁₂H₈N₂)]_n, the Cu^II cation has a four‐coordination environment completed by two N atoms from one 1,10‐phenanthroline (phen) ligand and two O atoms belonging to two di­hydrogen benzene‐1,2,4,5‐­tetra­carboxyl­ate anions (H₂TCB²⁻). There is a twofold axis passing through the Cu^II cation and the centre of the phen ligand. The [Cu(phen)]²⁺ moieties are bridged by H₂TCB²⁻ anions to form an infinite one‐dimensional coordination polymer with a zigzag chain structure along the c axis. A double‐chain structure is formed by hydrogen bonds between adjacent zigzag chains. Furthermore, there are π–π stacking inter­actions between the phen ligands, with an average distance of 3.64 Å, resulting in a two‐dimensional network structure.     

catena‐Poly[[[2,4‐dichloro‐6‐(pyridin‐2‐ylmethyl­iminomethyl)phenolato]copper(II)]‐μ‐thio­cyanato]

The title complex, [Cu(C₁₃H₉Cl₂N₂O)(NCS)]_n, is a novel thio­cyanate‐bridged polynuclear copper(II) compound. The Cu^II atom is five‐coordinated in a square‐pyramidal configuration, with one O and two N atoms of one Schiff base ligand and one terminal N atom of a bridging thio­cyanate ligand defining the basal plane, and one terminal S atom of another bridging thio­cyanate ligand occupying the axial position. The [2,4‐dichloro‐6‐(pyridin‐2‐ylmethyl­imino­methyl)­phenolato]­copper(II) moieties are linked by the bridging thio­cyanate ligands, forming polymeric chains running along the a axis.     

catena‐Poly­[[[aqua(2‐methyl‐4‐oxo‐4H‐pyran‐3‐olato‐κO3,O4)copper(II)]‐μ‐chloro] monohydrate]

In the title complex, {[Cu(C₆H₅O₃)Cl(H₂O)]·H₂O}_n, the Cu^II atom has a deformed square‐pyramidal coordination geometry formed by two O atoms of the maltolate ligand, two bridging Cl atoms and the coordinated water O atom. The Cu atoms are bridged by Cl atoms to form a polymeric chain. The deprotonated hydroxyl and ketone O atoms of the maltolate ligand form a five‐membered chelate ring with the Cu atom. Stacking interactions and hydrogen bonds exist in the crystal.     

Di‐μ‐aqua‐bis­[(N‐salicyl­idene‐β‐alaninato‐κ3O,N,O′)copper(II)] urea disolvate

Crystals of the title compound, [Cu₂(C₁₀H₉NO₃)₂(H₂O)₂]·2CH₄N₂O, consist of two (N‐salicyl­idene‐β‐alaninato‐κ³O,N,O′)copper(II) coordination units bridged by two water moieties to form a dimer residing on a crystallographic inversion center, along with two uncoordinated urea mol­ecules. The Cu^II atom has square‐pyramidal coordination, with three donor atoms of the tridentate Schiff base and an O atom of the bridging aqua ligand in the basal plane. The axial position is occupied by the second bridging water ligand at a distance of 2.5941 (18) Å. Hydro­gen bonds between mol­ecules of urea and the neighboring dimer units lead to the formation of a two‐dimensional grid of mol­ecules parallel to [101]. The superposition of the normals of the pyramidal base planes in the direction [100] indicates possible π–π interactions between the neighboring units.     

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[μ2‐chloro‐μ2‐1,4‐oxathiane‐κ2S:S‐copper(I)]

The title complex, [CuCl(C₄H₈OS)]_n, contains infinite spiral (CuS)_n chains linked by bridging Cl atoms into layers. The Cl atoms do not form polymeric fragments with Cu^I, but combine into isolated centrosymmetric Cu₂Cl₂ units. The compound is non‐isomorphous with the Br‐containing analogue, which contains Cu₈S₈ rings linked by Br atoms into chains. The O atom of the 1,4‐oxathiane mol­ecule does not realize its coordination abilities in the known copper(I)–halide complexes, while in copper(II)–halide complexes, oxathiane is coordinated via the S and O atoms. This falls into a pattern of the preferred inter­actions, viz. weak acid (Cu^I atom) with weak base (S atom) and harder acid (Cu^II atom) with harder base (O atom).     

Hexa‐μ‐chloro‐μ4‐oxo‐tetrakis­[(4,5‐di­hydro‐2‐methyl‐1,2‐thiazole‐κN)copper(II)]

The title compound, [Cu₄Cl₆O(C₄H₇NS)₄], was obtained by the reaction of CuCl₂·2H₂O with 2‐methyl‐2‐thia­zoline in methanol. The complex has twofold crystallographic symmetry and contains a tetrahedron of four Cu^II atoms coordinating a central μ₄‐O atom, with the six edges of the tetrahedron bridged by Cl atoms. Distance ranges are Cu—O 1.917 (4)–1.920 (4) and Cu—Cl 2.370 (2)–2.445 (2) Å.     

catena‐Poly[[{4‐bromo‐2‐[2‐(dimethyl­amino)ethyl­imino­methyl]­phenol­ato}­copper(II)]‐μ‐azido]

The title complex, [Cu(C₁₁H₁₄BrN₂O)(N₃)]_n, is an inter­esting azide‐bridged polynuclear copper(II) compound. The Cu^II atom is five‐coordinated in a square‐pyramidal configuration, with one O and two N atoms of one Schiff base and one terminal N atom of a bridging azide ligand defining the basal plane, and another terminal N atom of another bridging azide ligand occupying the axial position. The {4‐bromo‐2‐[2‐(dimethyl­amino)ethyl­imino­meth­yl]phenolato}copper(II) moieties are linked by the bridging azide ligands, forming polymeric chains running along the b axis. Adjacent chains are further linked by weak Br⋯Br inter­actions into a sheet.     

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.     

Di‐μ‐acetato‐bis­{[2,4‐dichloro‐6‐(2‐pyridylmethyl­imino­meth­yl)­phenol­ato]zinc(II)} and di‐μ‐thio­cyanato‐bis­{[2,4‐dichloro‐6‐(2‐pyridylmethyl­imino­meth­yl)phenolato]copper(II)}

The two title complexes, [Zn₂(C₁₃H₉Cl₂N₂O)₂(C₂H₃O₂)₂], (I), and [Cu₂(C₁₃H₉Cl₂N₂O)₂(NCS)₂], (II), are dinuclear Schiff base compounds. Both mol­ecules are located on crystallographic centres of inversion. In (I), the Zn^II atom is five‐coordinated in a trigonal–bipyramidal coordination, with one imine N atom of one Schiff base and two acetate O atoms defining the basal plane, and one O atom and one pyridine N atom of the Schiff base occupying the axial positions, while in (II), the Cu^II atom is five‐coordinated in a square‐pyramidal coordination, with one O and two N atoms of one Schiff base and one terminal N atom of a bridging thio­cyanate ligand defining the basal plane, and one terminal S atom of another bridging thio­cyanate ligand occupying the apical position. The different bridging ligands lead to the different coordinations of the complexes.