catena‐Poly[potassium [copper(II)‐μ‐isothiocyanato‐μ‐N‐salicylidene‐β‐alaninato(2–)]]

The title polymeric compound, catena‐poly­[dipotassium [bis­[μ‐N‐salicyl­idene‐β‐alaninato(2−)]‐κ⁴O,N,O′:O′′;κ⁴O′′:O,N,O′‐dicopper(II)]‐di‐μ‐iso­thio­cyanato‐κ²N:S;κ²S:N], {K[Cu(NCS)(C₁₀H₉NO₃)]}_n, consists of [iso­thio­cyanato(N‐salicyl­idene‐β‐alaninato)copper(II)]⁻ anions connected through the two three‐atom thio­cyanate (μ‐NCS) and the two anti,anti‐μ‐­carboxyl­ate bridges into infinite one‐dimensional polymeric anions, with coulombically interacting K⁺ counter‐ions with coordination number 7 constrained between the chains. The Cu^II atoms adopt a distorted tetragonal–bipyramidal coordination, with three donor atoms of the tridentate Schiff base and one N atom of the bridging μ‐NCS ligand in the basal plane. The first axial position is occupied by a thio­cyanate S atom of a symmetry‐related μ‐NCS ligand at an apical distance of 2.9770 (8) Å, and the second position is occupied by an O atom of a bridging carboxyl­ate group from an adjacent coordination unit at a distance of 2.639 (2) Å.     

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.     

Poly[(μ‐pentafluorobenzoato‐κ2O:O′)(pentafluorobenzoato‐κO)(μ‐pyrazine‐κ2N:N′)copper(II)]: a coordination polymer linked into a three‐dimensional network by intermolecular C—H...F—C interactions

In the title compound, [Cu(C₆F₅COO)₂(C₄H₄N₂)]_n, (I), the asymmetric unit contains one Cu^II cation, two anionic pentafluorobenzoate ligands and one pyrazine ligand. Each Cu^II centre is five‐coordinated by three O atoms from three independent pentafluorobenzoate anions, as well as by two N atoms from two pyrazine ligands, giving rise to an approximately square‐pyramidal coordination geometry. Adjacent Cu^II cations are bridged by a pyrazine ligand and two pentafluorobenzoate anions to give a two‐dimensional layer. The layers are stacked to generate a three‐dimensional supramolecular architecture via strong intermolecular C—H...F—C interactions, as indicated by the F...H distance of 2.38 Å.     

A novel three‐dimensional copper(II) coordination polymer with 1,4‐bis(1,2,4‐triazol‐1‐ylmeth­yl)benzene and thio­cyanate

In the title complex, poly[copper(II)‐di‐μ₂‐thio­cyanato‐μ₂‐1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene], [Cu(NCS)₂(C₁₂H₁₂N₆)]_n, the Cu^II atom lies on an inversion centre in a tetra­gonally distorted octa­hedral environment. Four N atoms from thio­cyanate and 1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene (bbtz) ligands fill the equatorial positions, and S atoms from symmetry‐related thio­cyanate ligands fill the axial positions. The benzene ring of the bbtz ligand lies about an inversion centre. Single thio­cyanate bridges link the Cu^II atoms into two‐dimensional sheets containing an unprecedented 16‐membered [Cu₄(μ‐NCS‐N:S)₄] ring. The bbtz ligands further link the two‐dimensional sheets into a three‐dimensional network.     

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.     

Crystal Structures,Magnetic Properties and Catecholase‐Like Activities of μ‐Alkoxo‐μ‐Carboxylato Double Bridged Dinuclear and Tetranuclear Copper(II) Complexes

One μ‐alkoxo‐μ‐carboxylato bridged dinuclear copper(II) complex, [Cu₂(L¹)(μ‐C₆H₅CO₂)] ( 1 )(H₃L¹ = 1,3‐bis(salicylideneamino)‐2‐propanol)), and two μ‐alkoxo‐μ‐dicarboxylato doubly‐bridged tetranuclear copper(II) complexes, [Cu₄(L¹)₂(μ‐C₈H₁₀O₄)(DMF)₂]·H₂O ( 2 ) and [Cu₄(L²)₂(μ‐C₅H₆O₄]·2H₂O·2CH₃CN ( 3 ) (H₃L² = 1,3‐bis(5‐bromo‐salicylideneamino)‐2‐propanol)) have been prepared and characterized. The single crystal X‐ray analysis shows that the structure of complex 1 is dimeric with two adjacent copper(II) atoms bridged by μ‐alkoxo‐μ‐carboxylato ligands where the Cu···Cu distances and Cu‐O(alkoxo)‐Cu angles are 3.5 11 Å and 132.8°, respectively. Complexes 2 and 3 consist of a μ‐alkoxo‐μ‐dicarboxylato doubly‐bridged tetranuclear Cu(II) complex with mean Cu‐Cu distances and Cu‐O‐Cu angles of 3.092 Å and 104.2° for 2 and 3.486 Å and 129.9° for 3 , respectively. Magnetic measurements reveal that 1 is strong antiferromagnetically coupled with 2J =‐210 cm^?1 while 2 and 3 exhibit ferromagnetic coupling with 2J = 126 cm^?1 and 82 cm^?1 (averaged), respectively. The 2J values of 1–3 are correlated to dihedral angles and the Cu‐O‐Cu angles. Dependence of the pH at 25 °C on the reaction rate of oxidation of 3,5‐di‐tert‐butylcatechol (3,5‐DTBC) to the corresponding quinone (3,5‐DTBQ) catalyzed by 1–3 was studied. Complexes 1–3 exhibit catecholase‐like active at above pH 8 and 25 °C for oxidation of 3,5‐di‐tert‐butylcatechol.     

Poly­[copper(I)‐μ‐bromo‐μ‐2,3‐di­methyl­pyrazine‐N:N′]

In the structure of the title compound, [CuBr(C₆H₈N₂)]_n, each Cu²⁺ cation is surrounded by two 2,3‐di­methyl­pyrazine ligands and two Br^? anions in a distorted tetrahedral arrangement. The Cu²⁺ cations and Br^? anions form (Cu₂Br₂)₂ rhomboid dimers located around a centre of inversion. The 2,3‐di­methyl­pyrazine ligands connect the Cu²⁺ cations in the dimers into sheets parallel to (010).     

阴离子在构筑吡啶酰胺－铜(II)配位超分子体系中的作用

Three complexes Cu（ppca）2（H2O）2（NO3）2 （1）, Cu2（μ-OH）2（ppca）2（H2O）4）·（ClO4）2 （2） and Cu2（μ-CH3COO）4（ppca）2（3） have been synthesized by the reaction of copper（Ⅱ） salts with N-phenyl-4-pyridinecarboxamide （ppca） and characterized. For anions, in complex 1, NO3^- coordinated with copper（Ⅱ）, in complex 2 perchlorate anion did not take part in coordination, the copper（Ⅱ） cations were connected by μ-OH to form a dinuclear unit, and complex 3 had a dimeric copper（Ⅱ） carboxylate paddle-wheel core. Noncovalent interactions linked these complexes to form supramolecular networks. Different coordinating modes of anions controlled modes of intennolecular interactions, which resulted in different final structures.     

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.     

Magnetic Interactions through Imidazolate‐Bridges: Synthesis,Spectroscopy, Crystal Structure and Magnetic Properties of μ‐Imidazolato‐Bridged Copper(II) Complexes

The synthesis, characterization and crystal structures of substituted imidazolate bridged binuclear copper(II) complexes, [Cu₂(dien)₂(L)](ClO₄)₃, where dien = diethylenetriamine, L = imidazolate (im^—) ( 1 ), 2‐methylimidazolate (mim^—) ( 2 ) and benzimidazolate (bim^—) ( 3 ), are reported. The copper(II) ions of 1 — 3 posses a square planar coordination environment with dien coordinating as a tridentate ligand and the fourth position being occupied by a nitrogen atom of the bridging μ‐imidazolato group. In all three compounds the tendency to form additional long apical bonds at the copper(II) ions to the oxygen atoms of the perchlorate anions is observed. Temperature depended susceptibility data of polycrystalline samples reveal an antiferromagnetic coupling of the copper(II) atoms in 1 — 3 with J = —63.8, —75.4 and —36.8 cm^—1, respectively. Significant changes for these coupling constants could not be observed for measurements on frozen aqueous solutions. ESR spectra for solids and frozen solutions are consistent with intramolecular antiferromagnetic exchange interaction between the metal ions. From the data reported it can be concluded that the predominate mechanism for transmitting exchange coupling through the imidazolate bridge is due to a σ exchange pathways.     

Investigations on the Structure Diversity and Thermal Degradation Behavior of CdII and ZnII Thiocyanato Coordination Compounds based on 3‐Acetylpyridine as Neutral Co‐Ligand

Reaction of Cd^II and Zn^II thiocyanate with 3‐acetylpyridine leads to the formation of the new Cd^II and Zn^II coordination compounds [Cd(NCS)₂(3‐acetylpyridine)₄] ( 1A ), [Cd(NCS)₂(3‐acetylpyridine)₂]_n ( 1B ), [Cd(NCS)₂(3‐acetylpyridine)]_n ( 1C ) and [Zn(NCS)₂(3‐acetylpyridine)₂] ( 2A ). Compound 1A consists of discrete complexes, in which the metal centers are octahedrally coordinated by four terminal bonded N‐donor co‐ligands and two terminal N‐bonded thiocyanato anions. In compound 2A the metal centers are only tetrahedrally coordinated by two terminal bonded N‐donor co‐ligands and two terminal N‐bonded thiocyanato anions. In compound 1B the Cd^II cations are octahedrally coordinated by two terminal bonded N‐donor co‐ligands and four thiocyanato anions. The metal centers are linked by μ‐1, 3 bridging thiocyanato anions into chains. In compound 1C the metal cations are octahedrally coordinated by two μ‐1, 5 bridging 3‐acetyl‐pyridine ligands and four μ‐1, 3 bridging thiocyanato anions building up a three‐dimensional coordination network. Investigations on the thermal degradation behavior of all compounds using simultaneous differential thermoanalysis and thermogravimetry as well as X‐ray powder diffraction and IR spectroscopy prove that on heating compound 2A decompose without the formation of 3‐acetylpyridine‐deficient intermediates. In contrast, for compound 1A a stepwise decomposition is observed, leading to the formation of the 3‐acetylpyridine‐deficient compound [Cd(NCS)₂(3‐acetylpyridine)₂]_n ( 1B ) which decomposes on further heating     

Di‐μ‐hydroxido‐bis{[bis(6‐methyl‐2‐pyridylmethyl)(2‐phenylethyl)amine‐κ3N′,N′′,N′′′]copper(II)} bis(perchlorate)

The title compund, [Cu₂(OH)₂(C₂₂H₂₅N₃)₂](ClO₄)₂, is a copper(II) dimer, with two [CuL]²⁺ units [L is bis(6‐methyl‐2‐pyridylmethyl)(2‐phenylethyl)amine] bridged by hydroxide groups to define the {[CuL](μ‐OH)₂[CuL]}²⁺ cation. Charge balance is provided by perchlorate counter‐anions. The cation has a crystallographic inversion centre halfway between the Cu^II ions, which are separated by 3.0161 (8) Å. The central core of the cation is an almost regular Cu₂O₂ parallelogram of sides 1.931 (2) and 1.935 (2) Å, with a Cu—O—Cu angle of 102.55 (11)°. The coordination geometry around each Cu^II centre can be best described as a square‐based pyramid, with three N atoms from L ligands and two hydroxide O atoms completing the coordination environment. Each cationic unit is hydrogen bonded to two perchlorate anions by means of hydroxide–perchlorate O—H...O interactions.     

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.     

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

The title complex, [Cu(C₁₁H₁₄BrN₂O)(NCS)]_n, is an inter­esting thio­cyanate‐bridged polynuclear copper(II) compound, which crystallizes with two independent mol­ecules in the asymmetric unit. Each Cu^II atom is five‐coordinate 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 apical position. The {4‐bromo‐2‐[2‐(dimethyl­amino)ethyl­imino­meth­yl]phenolato}copper(II) units are linked by the bridging thio­cyanate ligands, forming polymeric chains running along the a axis. There are weak inter­molecular C—H⋯O and C—H⋯S hydrogen bonds between the chains in the crystal structure.     

One‐dimensional zinc‐based coord­in­ation polymers incorporating cyanate anions

Two one‐dimensional zinc‐based coordination polymers containing cyanate anions are reported. catena‐Poly[sodium [[tricyanato­zinc(II)]‐μ‐1,4‐diaza­bicyclo­[2.2.2]octane‐κ²N:N′]], {Na[Zn(NCO)₃(C₆H₁₂N₂)]}_n, consists of linear [tricyanato­zinc(II)]‐μ‐1,4‐diaza­bicyclo­[2.2.2]octane strands in which the Zn²⁺ cations adopt trigonal–bipyramidal coordination on sites of m2 point symmetry. Na⁺ cations lie between the strands on sites of m point symmetry, coordinated in a distorted octa­hedral geometry by six O atoms of the cyanate anions. catena‐Poly[[dicyanato­zinc(II)]‐μ‐4,4′‐bipyridine‐κ²N:N′], [Zn(NCO)₂(C₁₀H₈N₂)]_n, crystallizes in the space group P2₁/n with Z′ = 5. The structure consists of zigzag strands formed by Zn²⁺ cations linked via 4,4′‐bipyridine. Each Zn²⁺ cation adopts a tetra­hedral coordination, with two sites occupied by 4,4′‐bipyridine and two cyanate anions completing the coordination sphere. The structure is closely comparable with the thio­cyanate and halide analogues [ZnX₂(C₁₀H₈N₂)] (X = NCS, Cl or Br).     

A one‐dimensional coordination polymer of 5‐[(imidazol‐1‐yl)methyl]benzene‐1,3‐dicarboxylic acid with CuII cations

5‐[(Imidazol‐1‐yl)methyl]benzene‐1,3‐dicarboxylic acid (H₂L) was synthesized and the dimethylformamide‐ and dimethylacetamide‐solvated structures of its adducts with Cu^II, namely catena‐poly[[copper(II)‐bis[μ‐3‐carboxy‐5‐[(imidazol‐1‐yl)methyl]benzoato]] dimethylformamide disolvate], {[Cu(C₁₂H₉N₂O₄)₂]·2C₃H₇NO}_n, (I), and catena‐poly[[copper(II)‐bis[μ‐3‐carboxy‐5‐[(imidazol‐1‐yl)methyl]benzoato]] dimethylacetamide disolvate], {[Cu(C₁₂H₉N₂O₄)₂]·2C₄H₉NO}_n, (II), the formation of which are associated with mono‐deprotonation of H₂L. The two structures are isomorphous and isometric. They consist of one‐dimensional coordination polymers of the organic ligand with Cu^II in a 2:1 ratio, [Cu(μ‐HL)₂]_n, crystallizing as the dimethylformamide (DMF) or dimethylacetamide (DMA) disolvates. The Cu^II cations are characterized by a coordination number of six, being located on centres of crystallographic inversion. In the polymeric chains, each Cu^II cation is linked to four neighbouring HL⁻ ligands, and the organic ligand is coordinated via Cu—O and Cu—N bonds to two Cu^II cations. In the corresponding crystal structures of (I) and (II), the coordination chains, aligned parallel to the c axis, are further interlinked by strong hydrogen bonds between the noncoordinated carboxy groups in one array and the coordinated carboxylate groups of neighbouring chains. Molecules of DMF and DMA (disordered) are accommodated at the interface between adjacent polymeric assemblies. This report provides the first structural evidence for the formation of coordination polymers with H₂Lvia multiple metal–ligand bonds through both carboxylate and imidazole groups.     

Polynuclear Chlorido Metal(II) Complexes with 1,2‐Di(1H‐­tetrazol‐1‐yl)ethane as Ligand Forming One‐ and Two‐dimensional Structures

The preparation and characterization of three metal(II) chlorido complexes with 1,2‐di(1H‐tetrazol‐1‐yl)ethane (dte) ( 1 ) as ligand is presented. The complexes have the following formula: [CoCl₂(μ‐dte)(dte)₂]_n ( 2 ), [CuCl₂(μ‐dte)₂]_n ( 3 ), and [Cd(μ‐Cl)₂(μ‐dte)]_n ( 4 ). Single crystal X‐ray diffraction of all three metal complexes was performed and the structures are discussed. All three central metal atoms are connected to polynuclear structures by the μ‐bridging ligand. Cobalt and copper are connected to one‐dimensional chains. The central cadmium(II) atoms are additionally connected by the chloride anions to a two‐dimensional network. Further, the cobalt(II) complex represents a special case with two terminal dte ligands.     

Ligand‐forced dimerization of copper(I)–olefin complexes bearing a 1,3,4‐thiadiazole core

As an important class of heterocyclic compounds, 1,3,4‐thiadiazoles have a broad range of potential applications in medicine, agriculture and materials chemistry, and were found to be excellent precursors for the crystal engineering of organometallic materials. The coordinating behaviour of allyl derivatives of 1,3,4‐thiadiazoles with respect to transition metal ions has been little studied. Five new crystalline copper(I) π‐complexes have been obtained by means of an alternating current electrochemical technique and have been characterized by single‐crystal X‐ray diffraction and IR spectroscopy. The compounds are bis[μ‐5‐methyl‐N‐(prop‐2‐en‐1‐yl)‐1,3,4‐thiadiazol‐2‐amine]bis[nitratocopper(I)], [Cu₂(NO₃)₂(C₆H₉N₃S)₂], (1), bis[μ‐5‐methyl‐N‐(prop‐2‐en‐1‐yl)‐1,3,4‐thiadiazol‐2‐amine]bis[(tetrafluoroborato)copper(I)], [Cu₂(BF₄)₂(C₆H₉N₃S)₂], (2), μ‐aqua‐bis{μ‐5‐[(prop‐2‐en‐1‐yl)sulfanyl]‐1,3,4‐thiadiazol‐2‐amine}bis[nitratocopper(I)], [Cu₂(NO₃)₂(C₅H₇N₃S₂)₂(H₂O)], (3), μ‐aqua‐(hexafluorosilicato)bis{μ‐5‐[(prop‐2‐en‐1‐yl)sulfanyl]‐1,3,4‐thiadiazol‐2‐amine}dicopper(I)–acetonitrile–water (2/1/4), [Cu₂(SiF₆)(C₅H₇N₃S₂)₂(H₂O)]·0.5CH₃CN·2H₂O, (4), and μ‐benzenesulfonato‐bis{μ‐5‐[(prop‐2‐en‐1‐yl)sulfanyl]‐1,3,4‐thiadiazol‐2‐amine}dicopper(I) benzenesulfonate–methanol–water (1/1/1), [Cu₂(C₆H₅O₃S)(C₅H₇N₃S₂)₂](C₆H₅O₃S)·CH₃OH·H₂O, (5). The structure of the ligand 5‐methyl‐N‐(prop‐2‐en‐1‐yl)‐1,3,4‐thiadiazol‐2‐amine (Mepeta ), C₆H₉N₃S, was also structurally characterized. Both Mepeta and 5‐[(prop‐2‐en‐1‐yl)sulfanyl]‐1,3,4‐thiadiazol‐2‐amine (Pesta ) (denoted L ) reveal a strong tendency to form dimeric {Cu₂L ₂}²⁺ fragments, being attached to the metal atom in a chelating–bridging mode via two thiadiazole N atoms and an allylic C=C bond. Flexibility of the {Cu₂(Pesta )₂}²⁺ unit allows the Cu^I atom site to be split into two positions with different metal‐coordination environments, thus enabling the competitive participation of different molecules in bonding to the metal centre. The Pesta ligand in (4) allows the Cu^I atom to vary between water O‐atom and hexafluorosilicate F‐atom coordination, resulting in the rare case of a direct Cu^I…FSiF₅²⁻ interaction. Extensive three‐dimensional hydrogen‐bonding patterns are formed in the reported crystal structures. Complex (5) should be considered as the first known example of a Cu^I(C₆H₅SO₃) coordination compound. To determine the hydrogen‐bond interactions in the structures of (1) and (2), a Hirshfeld surface analysis has been performed.     

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.     

Bis[N,N′‐(2‐chlorobenzylidene)ethylenediamine‐κ2N,N′]copper(I) dichloridocuprate(I) acetonitrile solvate

The 1:1 adduct of N,N′‐bis(2‐chlorobenzylidene)ethylenediamine (cb₂en) with copper(I) chloride proves to be an ionic compound with Cu^I‐centred cations and anions, [Cu(C₁₆H₁₄Cl₂N₂)₂][CuCl₂]·CH₃CN. In the cation, the Cu^I atom has a flattened tetrahedral coordination geometry, with a small bite angle for the chelating ligands, which form a double‐helical arrangement around the metal centre. The anion is almost linear, as expected. The packing of the cations involves intermolecular π–π interactions, which lead to columns of translationally related cations along the shortest unit‐cell axis, with anions and solvent molecules in channels between them.