Sb2Hg3GaBr4: A New Supramolecular Framework Structure with [Sb2Hg4/2]±0 Building Blocks Isosteric to Distibane

Sb₂Hg₃GaBr₄ is a new air stable transparent reddish solid that crystallizes in space group Pnma (No. 62, Z = 8) with the lattice constants a = 1375.49(8) pm, b = 1269.0(1) pm, c = 1478.19(9) pm. The title compound represents a new structure type based on a cationic framework of a significantly modified Millons base type. Structural building blocks of the cationic partial structure are well known tetrahedral [SbHg_4/2]⁺ groups and unprecedented formally neutral [Sb₂Hg_4/2]^±0 units in a 2:1 ratio. The [Sb₂Hg_4/2]^±0 units contain covalent Sb‐Sb bonds (d = 285.6 pm) and are isosteric with Distibane Sb₂H₄ in a staggered conformation. Structural consequences of the lone pairs located at the Sb atoms of the [Sb₂Hg_4/2]^±0 units are discussed. The charge of the cationic framework is balanced by disordered anions in suitable cavities. They appear as tetrahedral [GaBr₄]^? but correspond most likely to a superposition of bitetrahedral apex sharing [Ga₂Br₇]^? and isolated Br^?.     

Bis(1‐methyl­guanidinium) tetra­chloro­cuprate(II) and 4‐(2‐pyrimidin‐1‐io)­piperazinium tetra­chloro­cuprate(II)

The crystal structures of the title compounds, (C₂N₃H₈)₂[CuCl₄], (I), and (C₈H₁₄N₄)[CuCl₄], (II), have been studied by X‐ray diffraction. The structures consist of discrete [CuCl₄]^2? anions with two monoprotonated (C₂N₃H₈)⁺ cations for (I) and a diprotonated (C₈N₄H₁₄)²⁺ cation for (II). The [CuCl₄]^2? anions of both compounds have flattened tetrahedral geometries. There are several N—H?Cl weak bonds that join the [CuCl₄]^2? anions and the organic cations helping retain the pseudo‐tetrahedral geometries of the anions.     

{[Eu(ox)(H2O)4]·[CuBr(2‐pzc)2]·4H2O}: Hydrogen Bonding Directed Assembly to Supramolecular Network

A new 3d–4f heterometallic coordination framework, {[Eu(ox)(H₂O)₄] · [CuBr(2‐pzc)₂] · 4H₂O} ( 1 ) [ox = oxalate; 2‐pzc = pyrazine‐2‐carboxylate] was synthesized and characterized by elemental analysis, IR spectroscopy and thermal analysis, as well as single‐crystal X‐ray diffraction. Complex 1 represents one 3D supramolecular heterometallic coordination framework that is assembled from rare lanthanide‐ox anionic chains and CuBr(2‐pzc)₂ cationic units through hydrogen bonds.     

Synthesis,crystal structure and Raman spectra of [dabcoH2]CuICl3, [dabcoH2]3Cl4CuIICl4(DMSO) and Cu3Cl3(dabco)(DMSO) (dabco = 1,4-diazabicyclo [2.2.2] octane)

Dissolving elemental copper in a CCl₄–DMSO mixture in the presence of dabco (dabco = 1,4-diazabicyclo [2.2.2] octane) resulted in the formation of a compound with the composition [dabcoH₂][CuCl₃] featuring a univalent copper salt. This compound, composed of discrete dabcoH₂²⁺ cations and CuCl₃^2? anions, represents the first example of a copper(I) chloride derivative containing a doubly protonated [dabcoH₂]²⁺ unit, and a very rare example of the oxidative dissolving of copper in a CCl₄–DMSO mixture to give a Cu(I) compound. The addition of some drops of water to the initial reaction mixture led to the formation of the [dabcoH₂]₃Cl₄CuCl₄(DMSO). Three [dabcoH₂]²⁺ units and four Cl^? anions, bound via N–H…Cl hydrogen bonds, form a horseshoe-like cationic fragment. The divalent copper ion possesses a rather unusual pseudo-tetrahedral surrounding. The comproportionation reaction of CuCl₂·2H₂O and copper powder in the presence of dabco in DMSO results in the formation of the Cu₃Cl₃(dabco)(DMSO) complex. Copper and chlorine ions form unprecedented Cu₆Cl₆ cores, interconnected by neutral dabco linkers into infinite 2-D layers. All the compounds were characterized using the single-crystal X-ray diffraction technique and Raman spectroscopy.     

Preparation and crystal structure of bis(dibenzo-18-crown-6)-(tetrachlorocuprato(II)-Cl,Cl′, Cl″, Cl‴)dipotassium diaqua(dibenzo-18-crown-6)potassium dichlorocuprate(I)-dibenzo-18-crown-6

New mixed complex compound bis(dibenzo-18-crown-6)(tetrachlorocuprato(II)-Cl, Cl′, Cl″, Cl?) dipotassium diaqua(dibenzo-18-crown-6)potassium dichlorocuprate(I)dibenzo-18-crown-6 [(CuCl₄)[K(Db18C6)]₂]·[K(Db18C6)(H₂O)₂]⁺·[CuCl₂]^?·Db18C6 was prepared and its structure was studied by the X-ray structural analysis. The structure was found to be disordered. The asymmetric part of its unit cell contains 1/4 of each of its four components. For a given [CuCl₄]^2? anion its Cu²⁺ cation is disordered over two equally probable positions and its independent Cl atom is disordered over three positions differing by occupancy. In this structure two [K(Db18C6)]⁺ fragment of the complex molecule and the complex cation [K(Db18C6)(H₂O)₂]⁺ are of guest-host type with K⁺ cation as the guest. In this structure the statistically disordered alternating cations and Db18C6 molecules form infinite chains. The statistically disordered [CuCl₂]^? anions also form infinite chains.     

Three New Thioantimonates(V): Solvothermal Syntheses and Crystal Structures of [M(chxn)3]3(SbS4)2·4H2O (M = Ni,Co) and [Co(dien)2][Co(tren)SbS4]2·4H2O

The three new thioantimonates(V) [Ni(chxn)₃]₃(SbS₄)₂·4H₂O ( I ), [Co(chxn)₃]₃(SbS₄)₂·4H₂O ( II ) (chxn is trans‐1,2‐diaminocyclohexane) and [Co(dien)₂][Co(tren)SbS₄]₂·4H₂O ( III ) (dien is diethylenetriamine and tren is tris(2‐aminoethyl)amine) were synthesized under solvothermal conditions. Compounds I and II are isostructural crystallizing in space group C2/c. The structures are composed of isolated [M(chxn)₃]²⁺ complexes (M = Ni, Co), [SbS₄]^3? anions and crystal water molecules. Short S···N/S···O/O···O separations indicate hydrogen bonding interactions between the different constituents. Compound III crystallizes in space group and is composed of [Co(dien)₂]²⁺ and [Co(tren)SbS₄]^? anions and crystal water molecules. In the cationic complex the Co²⁺ ion is in an octahedral environment of two dien ligands whereas in [Co(tren)SbS₄]^? the Co²⁺ ion is in a trigonal bipyramidal coordination of four N atoms of tren and one S atom of the [SbS₄]^3? anion, i.e., two different coordination polyhedra around Co²⁺ coexist in this compound. Like in the former compounds an extended hydrogen bonding network connects the complexes and the water molecules into a three‐dimensional network.     

Trace Amounts of Aqueous Copper(II) Chloride Complexes in Hypersaline Solutions: Spectrophotometric and Thermodynamic Studies

Knowledge of the thermodynamic properties of aqueous copper(II) chloride complexes is important for understanding and quantitatively modeling trace copper behavior in hydrometallurgical extraction processing. In this paper, UV–Vis spectra data of Cu(II) chloride solutions with various salinities (NaCl, 0–5.57 mol·kg^?1) are collected at 25 °C. The concentration distribution of Cu–Cl species is in good agreement with those calculated by a reaction model (RM). The simple hydrated ion, Cu²⁺, is dominant at low concentration, whereas [CuCl]⁺, [CuCl₂]⁰ and [CuCl₃]^? become increasingly important as the chloride concentration rises. Moreover, the RM calculation suggests the present of a small amount of [CuCl₄]^2?. The de-convoluted molar spectrum of each species is in excellent agreement with our previous theoretical results predicted by time-dependent density functional theory treatment of aqueous Cu-containing systems. The formation constants for these copper chloride complexes have been reported and are to be preferred, except log₁₀ K ₂ ([CuCl₂]⁰).     

Diamondoid framework solid with Sn(OCH3)2–tetrapyridylporphyrin linkers,CuI nodes and [CuICl2]− counter‐ions

We report on the synthesis of a new metal–organic framework (MOF) composed of Sn(OCH₃)₂–tetrakis(pyridin‐4‐yl)porphyrin linkers, Cu⁺ connecting nodes and [CuCl₂]⁻ counter‐ions, namely poly[[bis(methanolato‐κO)[μ₅‐5,10,15,20‐tetrakis(pyridin‐4‐yl)porphyrin‐κ⁸1κN⁵:1′κN¹⁰:1′′κN¹⁵:1′′′κN²⁰:2κ⁴N²¹,N²²,N²³,N²⁴]copper(I)tin(II)] dichloridocuprate(I)], [CuSn(C₄₀H₂₄N₈)(CH₃O)₂][CuCl₂]. Its crystal structure consists of a single‐framework coordination polymer of the organic ligand and the Cu^I ions. The latter are characterized by a tetrahedral coordination geometry [with CN (coordination number) = 4], linking to the pyridyl N‐atom sites of four different ligands and imparting to the positively charged polymeric assembly a diamondoid PtS‐type topology. Correspondingly, every porphyrin unit is coordinated to four different Cu^I connectors. The [CuCl₂]⁻ anions occupy the intra‐lattice voids, along with disordered molecules of the water crystallization solvent. The asymmetric unit of this structure consists of two halves of the porphyrin scaffold, located on centres of crystallographic inversion, and the Cu⁺ and [CuCl₂]⁻ ions. This report provides unique structural evidence for the formation of tetrapyridylporphyrin‐based three‐dimensional MOFs with a diamondoid architecture that have been observed earlier only on rare occasions.     

Complexation in the CuCl2-C2H5OH-H2O system

Depending on the ethanol-water ratio, five individual compounds of copper(II) of the following compositions are formed in the CuCl₂-C₂H₅OH-H₂O system: [CuCl₂(C₂H₅OH)_4] (I), cis-[CuCl₂(C₂H₅OH)₂·(H₂O)₂] (II), trans-[CuCl₂(C₂H₅OH)₂· (H₂O)₂](III), [Cu(H₂O)₆]²⁺ (IV), and [Cu(OH)₂(H₂O)₄] (V).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2725–2729, December, 1990.     

Contacted Ion Pairs in Aqueous CuCl2 by the Combination of Ratio Spectra,Difference Spectra,Second Order Difference Spectra in the UV-Visible Spectra

The microstructure of aqueous CuCl₂ has been studied through lots of technologies for many years; however, it remains a controversial subject. In this study, a new spectroscopic method has been proposed to analyze the UV-visible spectra of thin film of CuCl₂/H₂O solutions at different concentrations. This method is the combination of ratio spectra, difference spectra and second order difference spectra. By using this method, two new bands at ~230 and ~380 nm are obviously observed. The bands are assigned as the contacted ion pairs[CuCl₃(H₂O)_n]^- or[CuCl₄(H₂O)_n]^2-, which demonstrates that ion pairs exist in the CuCl₂/H₂O solution. Such finding agrees with the recent theoretical spectra obtained by time-dependent density functional theory. Furthermore, the populations of the contacted ion pairs are discussed. This study not only offers the direct spectroscopic evidence of[CuCl₃(H₂O)_n]^- or[CuCl₄(H₂O)_n]^2- in aqueous CuCl₂, but also suggests that the spectroscopic analysis method is powerful to extract the weak bands in a strong overlapping spectrum.     

Synthesis and crystal structures of Cd[AlCl4]2 and Cd2[AlCl4]2

Colorless single crystals of Cd[AlCl₄]₂ grow from the melt of CdCl₂ and AlCl₃ upon slow cooling from 250°C. The crystal structure [monoclinic, P1a1, Z = 2, a = 1288.7(2), b = 660.2(1), c = 705.1(1) pm, β = 92.89(1)º] may be derived from hexagonally closest packed layers of Cl^?. Octahedral and tetrahedral holes are filled with Cd²⁺ and Al³⁺ in a 1:2 ratio between all layers stacked in the [104] direction. Cd[GaCl₄]₂ and Cd[AlBr₄]₂ are isotypic. Reduction of Cd[AlCl₄]₂ with excess cadmium shot and slow cooling from 350°C yields plate-like very moisture-sensitive, colorless single crystals of Cd₂[AlCl₄]₂. The crystal structure [triclinic, C1 , Z = 2, a = 655.47(3), b = 1135.26(1), c = 935.23(6) pm, α = 89.70(2)º, β = 103.61(1)º, γ = 90.455(1)º] is built from slabs stacked in the [100] direction consisting of ethane-like [Cd₂Cl₆] units with a Cd? Cd distance of 256.1 pm sharing common vertices with [AlCl₄] tetrahedra.     

First radical cation salts of 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) with copper(II) metal complex anions: β-(BDA-TTP)4Cu2Cl6 and (BDA-TTP)2CuCl4

New radical cation salts based on 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) with copper(II) metal complex anions, β-(BDA-TTP)₄Cu₂Cl₆ and (BDA-TTP)₂CuCl₄, were synthesized and structurally characterized. Single crystals were prepared by electrochemical oxidation of BDA-TTP under galvanostatic conditions. X-ray diffraction study demonstrated that the salts have a layered structure, in which the conducting BDA-TTP layers alternate with the [Cu₂Cl₆]²⁻ or [CuCl₄]²⁻ anions. Both salts show the semiconductor-type temperature dependence of the conductivity. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 48–54, January, 2007.     

[bmim]BF4/[Cu(Im12)2]CuCl2 as a novel catalytic reaction medium for click cyclization

Herein, a new application of an ionic liquid containing copper (I), ([Cu(Im¹²)₂]CuCl₂), is introduced. This ionic liquid was used as an efficient catalyst for the click cyclization between organic azides and terminal alkynes in various solvents. Then, the mixture of [bmim]BF₄/[Cu(Im¹²)₂]CuCl₂ was used as a green catalytic medium for the multicomponent click synthesis of 1,4-disubstituted-1H-1,2,3-triazoles from α-halo ketones. The reactions were performed efficiently in this mixture and excellent yields were obtained in all cases. This catalytic reaction medium was recycled five times without significant loss of activity.     

Structures of the complex ions [CuCl<Subscript>4</Subscript>]<Superscript>2−</Superscript> and [CuCl<Subscript>5</Subscript>]<Superscript>3−</Superscript>

The electronic structures of the complex ions [CuCl₄]^2? and [CuCl₅]^3? were analyzed in terms of the extended angular overlap model (AOM) with consideration to sd and pd mixing. The total antibonding orbital energies of these ions show no anomalies in the transition from a tetrahedron to a planar square [CuCl₄]^2? and from a trigonal bipyramid to a tetragonal pyramid [CuCl₅]^3?. Presumably, the existence of numerous intermediate forms of these complexes is mainly due to the packing effects rather than the electronic factors.     

1,1′‐Methylenedipyridinium tetrachloridocuprate(II) and bis[tetrachloridoaurate(III)] hybrid salts by X‐ray powder diffraction

In order to explore the potential propensity of the 1,1′‐methylenedipyridinium dication to form organic–inorganic hybrid ionic compounds by reaction with the appropriate halide metal salt, the organic–inorganic hybrid salts 1,1′‐methylenedipyridinium tetrachloridocuprate(II), (C₁₁H₁₂N₂)[CuCl₄], (I), and 1,1′‐methylenedipyridinium bis[tetrachloridoaurate(III)], (C₁₁H₁₂N₂)[AuCl₄]₂, (II), were obtained by treatment of 1,1′‐methylenedipyridinium dichloride with CuCl₂ and Na[AuCl₄], respectively. Both hybrid salts were isolated as pure compounds, fully characterized by multinuclear NMR spectroscopy and their molecular structures confirmed by powder X‐ray diffraction studies. The crystal structures consist of discrete 1,1′‐methylenedipyridinium dications and [CuCl₄]²⁻ and [AuCl₄]⁻ anions for (I) and (II), respectively. As expected, the dications form a butterfly shape; the Cu^II centre of [CuCl₄]²⁻ has a distorted tetrahedral configuration and the Au^III centre of [AuCl₄]⁻ shows a square‐planar coordination. The ionic species of (I) and the dication of (II) each have twofold axial symmetry, while the two [AuCl₄]⁻ anions are located on a mirror‐plane site. Both crystal structures are stabilized by intermolecular C—H...Cl hydrogen bonds and also by Cl...π interactions. It is noteworthy that, while the average intermolecular centroid–centroid pyridinium ring distance in (I) is 3.643 (8) Å, giving strong evidence for noncovalent π–π ring interactions, for (II), the shortest centroid–centroid distance between pyridinium rings of 5.502 (9) Å is too long for any significant π–π ring interactions, which might be due to the bulk of the two [AuCl₄]⁻ anions.     

具有可逆热致变色有机-无机杂化铜化合物的合成及表征

在浓盐酸水溶液中，碘化N，N-二甲基-1，5-二氮杂环[3.2.1]辛烷（[3.2.1-Me₂dabco]I₂）和碘化1-氨基-1，4-二氮杂环[2.2.2]辛烷（[2.2.2-NH₂dabco]I）与氯化铜反应得到2种有机-无机杂化铜化合物[3.2.1-Me₂dabco][CuCl₄]（1）和[2.2.2-NH₂dabco][CuCl₄]（2）。X射线单晶结构衍射证实化合物1和2中的无机阴离子是[CuCl₄]^2-四面体。化合物1和2表现出可逆的热致变色现象，随着温度升高，它们的颜色从黄色变为红色，这应该是由[CuCl₄]^2-四面体的变形引起的。     

The crystal structure of K2[Cu3ZnF(PO4)3], a new mixed zinc copper phosphate

The title compound has been prepared by hydrothermal synthesis and its crystal structure was determined by single crystal X-ray diffraction: space group P2₁/m, a = 4.8890(2), b = 14.3857(5), c = 7.9017(3) Å, β = 90.134(4)°, wR₂ = 0.123, R = 0.045. Cu²⁺ has two different coordination polyhedra: an elongated square pyramidal [CuFO₄] and square planar [CuO₄] coordination in a 2:1 ratio. Edge-sharing double-pyramids and [CuO₄] squares form zig-zag chains interconnected by [ZnO₄] and [PO₄] tetrahedra to form an open anionic framework structure whose channels are occupied by the K⁺ ions.     

A Novel Trinuclear Nickel(II) Phenanthroline Suberato Complex: {Ni[Ni(phen)(H2O)4]2L4/2}L · 4H2O (H2L = suberic acid)

The Reaction of freshly precipitated NiCO₃ with phenanthroline and suberic acid in CH₃OH/H₂O at room temperature gave the title complex consisting of polymeric {Ni[Ni(phen)(H₂O)₄]₂L_4/2}²⁺ cationic chains, suberate anions and hydrogen bonded H₂O molecules. The cationic chains are generated from bis‐monodentate suberato ligands bridging the trinuclear {Ni[Ni(phen)(H₂O)₄]₂}⁶⁺ groups, in which the central Ni atom is, via two μ‐H₂O molecules, coordinated to two monodentate cationic [Ni(phen)(H₂O)₄]²⁺ complex ligands at trans positions. The NiO₆ octahedral coordination about the central Ni atom is elongated tetragonally distorted with d(Ni—O) = 2.033—2.166Å and the NiN₂O₄ octahedra about the side Ni atoms are significantly distorted with d(Ni—N) = 2.089, 2.099Å, d(Ni—O) = 2.046—2.117Å. The polymeric cationic chains are assembled via π—π stacking interactions into open 2D layers, between which the suberate anions and crystal H₂O molecules are sandwiched. Crystal data: triclinic, P1¯ (no. 2), a = 11.397(2)Å, b = 11.975(2)Å, c = 12.500(2)Å, α = 107.75(1)°, β = 104.50(1)°, γ = 109.68(1)°, Z = 1, R = 0.0521, wR² = 0.1249 for 3892 out of 6198 reflections with F_o² > 2σ(F_o²).     

Synthesis of Two‐Electron Bimetallic Cu–Ag and Cu–Au Clusters by using [Cu13(S2CNnBu2)6(C≡CPh)4]+ as a Template

Atomically precise Cu‐rich bimetallic superatom clusters have been synthesized by adopting a galvanic exchange strategy. [Cu@Cu₁₂(S₂CNⁿBu₂)₆(C≡CPh)₄][CuCl₂] ( 1 ) was used as a template to generate compositionally uniform clusters [M@Cu₁₂(S₂CNⁿBu₂)₆ (C≡CPh)₄][CuCl₂], where M=Ag ( 2 ), Au ( 3 ). Structures of 1 , 2 and 3 were determined by single crystal X‐ray diffraction and the results were supported by ESI‐MS. The anatomies of clusters 1 – 3 are very similar, with a centred cuboctahedral cationic core that is surrounded by six di‐butyldithiocarbamate (dtc) and four phenylacetylide ligands. The doped Ag and Au atoms were found to preferentially occupy the centre of the 13‐atom cuboctahedral core. Experimental and theoretical analyses of the synthesized clusters revealed that both Ag and Au doping result in significant changes in cluster stability, optical characteristics and enhancement in luminescence properties.