catena‐Poly­[[[cis‐bis(1‐phenyl­tetra­zole‐κN4)copper(II)]‐di‐μ‐chloro] hemi(1‐phenyl­tetrazole)]

The title compound, {[CuCl₂(PhTz)₂]·0.5PhTz}_n (PhTz is 1‐­phenyl­tetrazole, C₇H₆N₄), has a polymeric structure, with uncoordinated disordered PhTz mol­ecules in the cavities. The coordination polyhedron of the Cu atom is a highly elongated octahedron. The equatorial positions are occupied by two Cl atoms [Cu—Cl = 2.2687 (9) and 2.2803 (7) Å] and two N atoms of the PhTz ligands [Cu—N = 2.0131 (19) and 2.0317 (18) Å]. The more distant axial positions are occupied by two Cl atoms [Cu—Cl = 3.0307 (12) and 2.8768 (11) Å] that lie in the equatorial planes of two neighbouring Cu octahedra. The [CuCl₂(PhTz)₂] units are linked by Cu—Cl bridges into infinite chains extending parallel to the a axis. The chains are linked into two‐dimensional networks by intermolecular C—H⋯N interactions between the phenyl and tetrazole fragments, and by face‐to‐face π–π interactions between symmetry‐related phenyl rings. These two‐dimensional networks, which lie parallel to the ac plane, are connected by intermolecular π–π stacking interactions between phenyl rings, thus forming a three‐dimensional network.     

Unusual 4‐arsonoanilinium cationic species in the hydrochloride salt of (4‐aminophenyl)arsonic acid and formed in the reaction of the acid with copper(II) sulfate,copper(II) chloride and cadmium chloride

Structures having the unusual protonated 4‐arsonoanilinium species, namely in the hydrochloride salt, C₆H₉AsNO₃⁺·Cl⁻, (I), and the complex salts formed from the reaction of (4‐aminophenyl)arsonic acid (p‐arsanilic acid) with copper(II) sulfate, i.e. hexaaquacopper(II) bis(4‐arsonoanilinium) disulfate dihydrate, (C₆H₉AsNO₃)₂[Cu(H₂O)₆](SO₄)₂·2H₂O, (II), with copper(II) chloride, i.e. poly[bis(4‐arsonoanilinium) [tetra‐μ‐chlorido‐cuprate(II)]], {(C₆H₉AsNO₃)₂[CuCl₄]}_n , (III), and with cadmium chloride, i.e. poly[bis(4‐arsonoanilinium) [tetra‐μ‐chlorido‐cadmate(II)]], {(C₆H₉AsNO₃)₂[CdCl₄]}_n , (IV), have been determined. In (II), the two 4‐arsonoanilinium cations are accompanied by [Cu(H₂O)₆]²⁺ cations with sulfate anions. In the isotypic complex salts (III) and (IV), they act as counter‐cations to the {[CuCl₄]²⁻}_n or {[CdCl₄]²⁻}_n anionic polymer sheets, respectively. In (II), the [Cu(H₂O)₆]²⁺ ion sits on a crystallographic centre of symmetry and displays a slightly distorted octahedral coordination geometry. The asymmetric unit for (II) contains, in addition to half the [Cu(H₂O)₆]²⁺ ion, one 4‐arsonoanilinium cation, a sulfate dianion and a solvent water molecule. Extensive O—H…O and N—H…O hydrogen bonds link all the species, giving an overall three‐dimensional structure. In (III), four of the chloride ligands are related by inversion [Cu—Cl = 2.2826 (8) and 2.2990 (9) Å], with the other two sites of the tetragonally distorted octahedral CuCl₆ unit occupied by symmetry‐generated Cl‐atom donors [Cu—Cl = 2.9833 (9) Å], forming a two‐dimensional coordination polymer network substructure lying parallel to (001). In the crystal, the polymer layers are linked across [001] by a number of bridging hydrogen bonds involving N—H…Cl interactions from head‐to‐head‐linked As—O—H…O 4‐arsonoanilinium cations. A three‐dimensional network structure is formed. Cd^II compound (IV) is isotypic with Cu^II complex (III), but with the central CdCl₆ complex repeat unit having a more regular M —Cl bond‐length range [2.5232 (12)–2.6931 (10) Å] compared to that in (III). This series of compounds represents the first reported crystal structures having the protonated 4‐arsonoanilinium species.     

catena‐Poly­[[bis­[μ‐1,2‐bis(1‐methyl­tetrazol‐5‐yl)­ethane‐κ2N4:N4′]bis[chloro­copper(II)]]‐di‐μ‐chloro]

In the title compound, [Cu₂Cl₄(C₆H₁₀N₈)₂]_n, the ligand has C₂ symmetry, and the Cu and Cl atoms lie on a mirror plane. The coordination polyhedron of the Cu atom is a distorted square pyramid, with the basal positions occupied by two N atoms from two different ligands [Cu—N = 2.0407 (18) Å] and by the two Cl atoms [Cu—Cl = 2.2705 (8) and 2.2499 (9) Å], and the apical position occupied by a Cl atom [Cu—Cl = 2.8154 (9) Å] that belongs to the basal plane of a neighbouring Cu atom. The [CuCl₂(C₆H₁₀N₈)]₂ units form infinite chains extending along the a axis via the Cl atoms. Intermolecular C—H⃛Cl contacts [C⃛Cl = 3.484 (2) Å] are also present in the chains. The chains are linked together by intermolecular C—H⃛N interactions [C⃛N = 3.314 (3) Å].     

Crystal Structure of a Cadmium Iodate Monohydrate: Cd(IO3)2·H2O

Single crystals of Cd(IO₃)₂·H₂O are obtained by slow evaporation of aqueous solutions of CdCl₂ and KIO₃. This compound crystallizes in the triclinic space group P1¯ [a = 7.119(2), b = 7.952(2), c = 6.646(2)Å, α = 102.17(2)°, β = 114.13(2)°, γ = 66.78(4)°]. The structure consists in Cd — (μ2‐O)₂ — Cd dimers with a metal — metal distance of 3.74Å. These dimers are connected through two iodate bridges resulting in layers parallel to the (010) plane. The 3D linkage is ensured by I1 — O1 long bonds (2.775Å).     

A three‐dimensional supramolecular network built with the zigzag chain complex bis(5‐carboxy‐1H‐imidazole‐4‐carboxyl­ato)copper(II)

In the title complex, poly[copper(II)‐di‐μ‐5‐carboxy‐1H‐imidazole‐4‐carboxyl­ato], [Cu(C₅H₃N₂O₄)₂]_n or [Cu(H₂Imda)₂]_n, each imidazole moiety is bonded to the Cu atom via O and N atoms to give a square‐planar coordination [Cu—O = 2.014 (2) and 2.016 (2) Å, and Cu—N = 1.982 (3) and 1.992 (2) Å]. The distorted square‐pyramidal geometry at the Cu atom results from coordination to an adjacent O atom [Cu—O = 2.305 (2) Å], which generates zigzag chains. There is a sixth, weaker, octahedral coordination to the Cu atom from an inversion‐related O atom [Cu—O = 3.090 (2) Å], which links the chains into sheets in the (100) plane. Imidazole moieties in the sheets are linked in the [100] direction by pairs of N—H⋯O and C—H⋯O hydrogen bonds, thus generating a three‐dimensional network.     

Two Novel CuII Phenanthroline Adipato Complexes with π‐π Stacking Interactions: [Cu(phen)2(C6H8O4)] · 4.5 H2O and [(Cu2(phen)2Cl2)(C6H8O4)] · 4 H2O

The blue copper complex compounds [Cu(phen)₂(C₆H₈O₄)] · 4.5 H₂O ( 1 ) and [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)] · 4 H₂O ( 2 ) were synthesized from CuCl₂, 1,10‐phenanthroline (phen) and adipic acid in CH₃OH/H₂O solutions. [Cu(phen)₂‐ (C₆H₈O₄)] complexes and hydrogen bonded H₂O molecules form the crystal structure of ( 1 ) (P1 (no. 2), a = 10.086(2) Å, b = 11.470(2) Å, c = 16.523(3) Å, α = 99.80(1)°, β = 115.13(1)°, γ = 115.13(1)°, V = 1617.5(5) ų, Z = 2). The Cu atoms are square‐pyramidally coordinated by four N atoms of the phen ligands and one O atom of the adipate anion (d(Cu–O) = 1.989 Å, d(Cu–N) = 2.032–2.040 Å, axial d(Cu–N) = 2.235 Å). π‐π stacking interactions between phen ligands are responsible for the formation of supramolecular assemblies of [Cu(phen)₂(C₆H₈O₄)] complex molecules into 1 D chains along [111]. The crystal structure of ( 2 ) shows polymeric [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains (P1 (no. 2), a = 7.013(1) Å, b = 10.376(1) Å, c = 11.372(3) Å, α = 73.64(1)°, β = 78.15(2)°, γ = 81.44(1)°, V = 773.5(2) ų, Z = 1). The Cu atoms are fivefold coordinated by two Cl atoms, two N atoms of phen ligands and one O atom of the adipate anion, forming [CuCl₂N₂O] square pyramids with an axial Cl atom (d(Cu–O) = 1.958 Å, d(Cu–N) = 2.017–2.033 Å, d(Cu–Cl) = 2.281 Å; axial d(Cu–Cl) = 2.724 Å). Two square pyramids are condensed via the common Cl–Cl edge to centrosymmetric [Cu₂Cl₂N₄O₂] dimers, which are connected via the adipate anions to form the [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains. The supramolecular 3 D network results from π‐π stacking interactions between the chains. H₂O molecules are located in tunnels.     

Hexa‐μ2‐chloro‐μ4‐oxo‐tetrakis[(2‐ethyl­tetrazole‐κN4)copper(II)]

In the title molecular complex, [Cu₄Cl₆O(2‐EtTz)₄], where 2‐EtTz is 2‐ethyl­tetrazole (C₃H₆N₄), the central O atom is located on the symmetry site and is tetrahedrally coordinated to four Cu atoms, with Cu—O distances of 1.8966 (4) Å. A very slight distortion of Cu₄O from a regular tetrahedron is observed [two Cu—O—Cu angles are 108.76 (3)° and four others are 109.828 (13)°]. Each Cu atom is connected to three others via the Cl atoms, forming a slightly distorted Cl octahedron around the O atom, with O⋯Cl distances of 2.9265 (7) Å for Cl atoms lying on the twofold axis and 2.9441 (13) Å for those in general positions. The Cu atom has a distorted trigonal–bipyramidal environment, with three Cl atoms in the equatorial plane, and with the N atom of the 2‐ethyl­tetrazole ligand and the μ₄‐O atom in axial positions. The Cu atom is displaced out of the equatorial plane by ca 0.91 Å towards the coordinated N atom of the 2‐­ethyl­tetrazole ligand.     

The layered structure of poly­[[di‐μ‐chloro‐bis­[chloro(2‐ethyl­tetrazole‐κN4)copper(II)]]‐di‐μ‐2‐ethyl­tetrazole‐κ2N1:N4]

In the polymeric title complex, [CuCl₂(C₃H₆N₄)₂]_n, there are two ligands in the asymmetric unit. The Cu atom adopts an elongated octahedral geometry, with two 2‐ethyl­tetrazole ligands [Cu—N = 2.0037 (16) and 2.0136 (16) Å] and two Cl atoms [Cu—Cl = 2.2595 (6) and 2.2796 (6) Å] in equatorial positions. A Cl atom and a symmetry‐related 2‐ethyl­tetrazole mol­ecule [Cu—Cl = 2.8845 (8) Å and Cu—N = 2.851 (2) Å] lie in the axial positions of the octahedron. One of the two 2‐­ethyltetrazole ligands of the asymmetric unit exhibits bidentate binding to two Cu atoms through two N atoms of the tetrazole ring, whereas the other ligand is coordinated in a monodentate fashion via one tetrazole N atom. The Cu‐atom octahedra form dimer entities by sharing edges with equatorial and axial Cl atoms. The dimers are linked together through the 2‐ethyl­tetrazole ligands to form one‐dimensional polymeric zigzag chains extending along the b axis. The chains are connected into infinite layers parallel to the (10) plane via the 2‐ethyl­tetrazole ligands.     

catena‐Poly[[bis(cis‐1‐tert‐butyltetrazole‐κN4)copper(II)]‐di‐μ‐chloro]

The title polymeric compound, [CuCl₂(C₅H₁₀N₄)₂]_n, is the first structurally characterized complex with a bulky 1‐alkyl­tetrazole ligand. The coordination polyhedron of the Cu atom is an elongated octahedron. The equatorial positions of the octahedron are occupied by the two Cl atoms, with Cu—Cl distances of 2.2920 (8) and 2.2796 (9) Å, and by the two N‐4 atoms of the tetrazole ligands, with Cu—N distances of 2.023 (2) and 2.039 (2) Å. Two symmetry‐related Cl atoms occupy the axial positions, at distances of 2.8244 (8) and 3.0174 (8) Å from the Cu atom. The [CuCl₂(C₅H₁₀N₄)₂] units form infinite chains extended along the b axis, linked together only by van der Waals interactions. The skeleton of each chain consists of Cu and Cl atoms.     

[1,5-Bis(1-methyl-1H-tetrazol-5-yl-κN)-3-oxopentane-κO]dichlorocopper(II)

The title compound, [CuCl₂(C₈H₁₄N₈O)], is the first structurally characterized molecular chelate complex of a binuclear N-substituted tetrazole. The Cu atom is five-coordinate, with an approximately square-pyramidal geometry. The equatorial positions of the pyramid are occupied by two Cl atoms and two N atoms from the ligand mol­ecule; the O atom of the ligand lies in the axial position. Each complex is connected to four others via weak C—H⋯Cl and C—H⋯N interactions, forming sheets parallel to the (010) plane.     

Di­chloro­bis(2‐chloro‐5‐methyl­pyridine‐κN)copper(II)

In the crystals of the title compound, [CuCl₂(C₆H₆ClN)₂], the Cu atom lies on an inversion centre and is four‐coordinated by two pyridine N atoms and two Cl atoms in trans positions. The coordination geometry is square planar, with Cu—N and Cu—Cl distances of 1.986 (2) and 2.2536 (11) Å, respectively. The two pyridine rings are parallel, but twist from the CuN₂Cl₂ coordination plane by about 95° in the complex mol­ecule. There are three kinds of intermolecular C—H⃛Cl hydrogen bonds in the crystals. Two of these types generate two‐dimensional molecular networks, viewed in the direction of the a axis, and the other connects adjacent molecular networks.     

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.     

π-Complexes of Cu(I) with Alkynes. Synthesis and Crystal Structure of Cs[CuCl<Subscript>2</Subscript>(HOCH<Subscript>2</Subscript>C≡CCH<Subscript>2</Subscript>OH)] ⋅ H<Subscript>2</Subscript>O

Crystals of anionic π-complex Cs[CuCl₂(HOCH₂C≡CCH₂OH)] ? H₂O were synthesized by reaction of 2-butyne-1,4-diol with CuCl in a saturated aqueous solution of CsCl at 90°C and studied by X-ray diffraction analysis. The crystals are triclinic (space group \(P\bar 1\) ; a = 10.155(4) Å, b = 7.828(4) Å, c = 7.115(3) Å, α = 102.62(4)°, β = 100.77(3)°, γ = 106.71(4)°, V = 509(1) ų, Z = 2) and consist of stacks of individual anions [CuCl₂(HOCH₂C≡CCH₂OH)]^? and hydrated [Cs ? H₂O]⁺ cations between the stacks. The Cu(I) atom has trigonal surrounding of two Cl atoms and the C≡C bond of 2-butyne-1,4-diol molecule. The Cu-(C≡C) distance in the π-core is 1.905(8) Å; the C≡C bond is elongated to 1.223(11) Å. In addition to hydrogen bonds O-H?Cl, crystals of the complex also contain O(w)?H-O and O(w)?Cl bonds stabilizing their structure.     

Hirshfeld Surface Analysis,Crystal Structure and Spectroscopic Studies of a New Cu(II) Halocuprate Salt with Protonated N-Amino-Ethyl-Piperazine

(C₆H₁₈N₃)₄[CuCl₅]₂[CuCl₄]₃·1.42H₂O is prepared and characterized by various physicochemical techniques. The single crystal X-ray diffraction structural analysis reveals that the title compound belongs to the orthorhombic system with the space group Cmca. Its unit cell dimensions are: a = 24.286(2) Å, b = 14.3082(14) Å, c = 16.6160(16) Å, Z = 4, V = 5773.8(10) ų. Its crystal structure is determined and refined down to R = 0.024 and wR(F²) = 0.059. The structure contains three crystallographically independent Cu²⁺ ions coordinated to chlorine anions in various fashions. Cu1 is five-coordinated in a distorted square pyramidal fashion, while Cu2 and Cu3 are four-coordinated in square planar and distorted tetrahedral fashions, respectively. The entities are interconnected by means of the hydrogen bonding [O(W)–H…Cl, N–H…Cl, C–H…Cl and C–H…O(W)], forming a three-dimensional network. Intermolecular interactions are investigated by Hirshfeld surfaces and the contacts of the eight different chloride atoms are notably compared. The vibrational absorption bands are identified by infrared spectroscopy. The optical study is performed by UV-vis absorption.     

Dichloro­(O‐ethyl 3‐methyl­pyridine‐2‐carboximidic acid‐κ2N,N′)copper(II)

In the title compound, [CuCl₂(C₉H₁₂N₂O)], the Cu^II atom is coordinated by two Cl⁻ anions and two N atoms of one O‐ethyl 3‐methyl­pyridine‐2‐carboximidic acid mol­ecule in a slightly distorted square‐planar geometry, with Cu—N distances of 2.0483 (17) and 1.9404 (18) Å, and Cu—Cl distances of 2.2805 (10) and 2.2275 (14) Å. In addition, each Cu^II atom is connected by one Cl⁻ anion and the Cu^II atom from a neighbouring mol­ecule, with Cu⋯Cl and Cu⋯Cu distances of 2.9098 (13) and 3.4022 (12) Å, respectively, and, therefore, a centrosymmetric dimer is formed. Adjacent mol­ecular dimers are connected by π–π stacking inter­actions between pyridine rings to form a zigzag mol­ecular chain. The mol­ecular chains are also enforced by N—H⋯Cl and C—H⋯Cl inter­actions.     

(+ac,−ac)‐trans‐Bis(hinokitiolato)copper(II) and its chloroform disolvate

The complex trans‐bis(hinokitiolato)copper(II) [systematic name: trans‐bis(3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trienolato)copper(II); abbreviated name: trans‐Cu(hino)₂], [Cu(C₁₀H₁₁O₂)₂], is a biologically active compound. Three polymorphs of this square‐planar monomer, all with (+sp,−sp) isopropyl substituents, have been reported previously. A fourth polymorph containing (+ac,−ac) isopropyl groups and its chloroform disolvate, [Cu(C₁₀H₁₁O₂)₂]·2CHCl₃, both exhibiting nonmerohedral twinning and with all Cu atoms on centers of crystallographic inversion symmetry, are reported here. One of the differences between all of these polymorphs is the relative conformation of the isopropyl groups with respect to the plane of the molecule. Stacking and Cu...olefin π distances ranging from 3.214 (4) to 3.311 (2) Å are observed, and the chloroform solvent molecules participate in bifurcated C—H...O hydrogen bonds [H...O = 2.26–2.40 Å, C...O = 3.123 (5)–3.214 (5) Å, C—H...O = 127–151° and O...H...O = 74°].     

Aqua­chloro(1,10‐phenanthroline‐κ2N,N′)(p‐toluenesulfonato‐κO)copper(II)

In the title compound, [CuCl(C₇H₇O₃S)(C₁₂H₈N₂)(H₂O)], the central Cu atom is coordinated by a water mol­ecule, a chloride ion, an O‐monodentate p‐toluene­sulfonate anion and an N,N′‐bidentate 1,10‐phenanthroline ligand. The copper environment is best described as a slightly distorted square pyramid, with bond distances Cu—Cl 2.2282 (9) Å, Cu—OW 1.984 (3) Å, and Cu—N 2.006 (3) and 2.028 (3) Å; the apical Cu—O distance is 2.281 (2) Å. In the supramolecular structure, π–π‐stacking stabilization is observed, and classical and non‐classical hydrogen bonds also play an important role.     

Dichloro­[(1E,1′E)‐1,1′‐(pyridine‐2,6‐diyl)diethanone bis­(O‐methyl­oxime)‐κ3N1,N2,N6]copper(II)

In the title compound, [CuCl₂(C₁₁H₁₅N₃O₂)], the Cu^II ion is five‐coordinated in a strongly distorted trigonal–bipyramidal arrangement, with the two methyl­oxime N atoms located in the apical positions, and the pyridine N and the Cl atoms located in the basal plane. The two axial Cu—N distances are almost equal (mean 2.098 Å) and are substantially longer than the equatorial Cu—N bond [1.9757 (15) Å]. It is observed that the N(oxime)—M—N(pyridine) bond angle for five‐membered chelate rings of 2,6‐diacetyl­pyridine dioxime complexes is inversely related to the magnitude of the M—N(pyridine) bond. The structure is stabilized by intra‐ and inter­molecular C—H⋯Cl hydrogen bonds which involve the methyl H atoms, except for one of the two acetyl­methyl groups.     

A Zipper‐like Supramolecular Double‐Chain based on 1 D π‐π Stacking Interactions: Synthesis and Crystal Structure of [Cu(phen)(C4H4O4)(H2O)]2 · C4H6O4 (phen = 1,10‐phenanthroline)

[Cu(C₁₂H₈N₂)(C₄H₄O₄)(H₂O)]₂ · C₄H₆O₄ was prepared by the reaction of succinic acid, CuCl₂ · 2 H₂O, 1,10‐phenanthroline (phen = C₁₂H₈N₂), and Na₂CO₃ in a CH₃OH–H₂O solution. The crystal structure (triclinic, P 1 (no. 2), a = 7.493(1), b = 9.758(1), c = 13.517(1) Å; α = 68.89(1)°, β = 88.89(1)°, γ = 73.32(1)°, Z = 1, R = 0.0308, wR² = 0.0799 for 3530 observed reflections (F ≥ 2σ(F ) out of 3946 unique reflections) consists of hydrogen bonded succinic acid molecules and succinato bridged 1 D zipperlike supramolecular [Cu(phen)(C₄H₄O₄)_2/2(H₂O)]₂ double chains based on 1 D π‐π stacking interactions between the chelating phen systems at distances of 3.71 Å and 3.79 Å. The Cu atoms are fivefold trigonal bipyramidally coordinated by two N atoms of the bidentate chelating phen ligand and three O atoms of one water molecule and two bidentate bridging succinate ligands. The water O atom and one phen N atom are at the apical positions (equatorial: d(Cu–O) = 1.945, 2.254(2) Å, d(Cu–N) = 2.034(2) Å; axial: d(Cu–O) = 1.971(2) Å, d(Cu–N) = 1.995 Å).     

Astemizole tetra­chloro­cuprate(II)

The structure of {3‐[(4‐fluoro­phenyl)­methyl]‐1H‐benzimidazol‐2‐ylidene}{1‐[2‐(4‐meth­oxy­phenyl)­ethyl]‐4‐piperidin‐1‐io}ammonium tetra­chloro­cuprate(II), (C₂₈H₃₃FN₄O)[CuCl₄], contains diprotonated cations of astemizole hydrogen bonded to three Cl atoms in two different CuCl₄^2? anions, with Cl?N distances in the range 3.166 (4)–3.203 (4) Å. The geometry around copper is flattened tetrahedral with significantly different Cu—Cl distances which lie in the range 2.1968 (14)–2.2861 (12) Å. The phenyl­ethyl C atoms of the (4‐methoxy­phenyl­)ethyl group are disordered indicating the presence of two conformers in the crystals.