[Cu4Cl4(C10H16S4)2]的合成和晶体结构

早有文献[1]报导，二硫代乙酸丙酮C5H8S2(记为SacSac）能以下列三种形式存在于金属配合物中：（I）（SacSac）2M，如M=Ni，Co等，其中SacSac呈负一价，通过两个S原子和金属直接螫合；（11）（SacSaChMCI。；如M二Mn，CdSn等，（S。Sac）呈正一价，且以阳离子状态存在干晶体和溶     

Crystal structure of [Co(NH3)5Cl]2(W10O32)·4H2O

By single crystal X-ray diffraction the crystal structure of the complex salt [Co(NH₃)₅Cl]₂(W₁₀O₃₂)·4H₂O is determined and the IR spectrum is interpreted. The crystal chemical analysis of the structure of complex cations and decatungstate anions and their packing in the structure is performed.     

原子簇化合物[Et4N]2[Mo2O2S2(S2)(S4)]的合成和结构

目前,Mo-S化合物的化学,特别是以多硫基为配体的铟硫化合物的化学是一个活跃的研究领域。这里我们报道含S₂^2-、S₄^2-两种多硫基的二核钼原子簇化合物〔Et₄N〕₂〔Mo₂O₂(S₂)(S₄)(u₃-S)₂]的合成和单晶结构。     

The unusual stability of [NpO2Cl4]2−: Synthesis and characterisation of [NpO2(DPPMO2)2Cl]2[NpO2Cl4] and [Ph3PNH2]2[NpO2Cl4]

The [NpO₂(DPPMO₂)₂Cl][NpO₂Cl₄] complex (where DPPMO₂ = bis(diphenylphosphino)methanedioxide) contains the linear neptunyl group, {NpO₂}²⁺, with two bidentate P=O donor ligands. Coordinating anion Cl^? fills the fifth equatorial coordination site yielding a complex of general formula [NpO₂(DPPMO₂)₂X]₂[Y] (1) (where X = Cl^? and Y = [NpO₂Cl₄]^2?. Reaction between our newly prepared neptunium starting material [NpO₂Cl₂(thf)]_n and phosphinimine ligand produced crystals of [Ph₃PNH₂]₂[NpO₂Cl₄] (2). Compounds 1 and 2 have been structurally characterised.     

Chlorine reaction with platinum triamine [Pt(N,N-DimeTm)PyCl3]Cl (N,N-DimeTm = (CH3)2N(CH2)3NH2). Crystal structure of [Pt(N,N-DimeTm)Cl2], [Pt(N,N-DimeTm(Py)Cl3]Cl · H2O and [Pt{(CH3)2N(CH2)2C(O)NH}(Py)Cl3]

Treatment of platinum(II) diamine [Pt(N,N-DimeTm)Cl₂] (I) with pyridine gave tetramine [Pt(N,N-DimeTm)Py₂]Cl₂ (II); by oxidation with chlorine this was converted to Pt(IV) triamine, [Pt“(N,N-DimeTm(Py)Cl₃]Cl (III) with a six-membered chelate ring. According to X-ray diffraction data, the reaction of complex II with chlorine is accompanied by removal of the pyridine molecule from the trans-position to the NH₂ group of N,N-dimethyltrimethylenediamine. The reaction of complex III with chlorine at 20°C afforded a mixture of compounds (IV) and the complex [Pt“(CH₃)₂N(CH₂)₂C(O)NH”(Py)Cl₃] (V) with an amidate six-membered metal ring, dimethylpropioamide, which was also isolated upon refluxing a mixture of IV in an aqueous solution. The UV/Vis and IR spectra of the obtained complexes were studied, and X-ray diffraction analysis of I, III, and V was performed. The crystals of I are triclinic, space group P $ \bar 1 $ ; a = 7.6526(4) Å, b = 11.5571(6) Å, c = 12.4432(7) Å, α = 113.85(1)°, β = 96.54(2)°, γ = 106.78(2)°; Z = 4; R _hkl = 0.051. The crystals of III are monoclinic, space group C2/c; a = 36.715(2) Å, b = 7.8179(4) Å, c = 29.721(16) Å, β = 127.80(1)°; Z = 16; R _hkl = 0.036. The crystals of V are monoclinic, space group P2₁/n; a = 7.0398(6) Å, b = 27.458(2) Å, c = 7.687(6) Å, β = 106.270(1)°; Z = 4; R _hkl = 0.052.     

簇合物[Et4N]2[Mo2S4(SCH2CH2S)2]的合成及晶体结构

以(NH4)2MoS4,Et4NBr,HSCH2CH2SH为原料合成了新的簇合物——[Et4N]2[Mo2S4(SCH2CH2S)2],其结构经X射线四圆衍射仪,IR。UV及元素分析确证。其晶体属单斜晶系。晶胞参数为：a=1．0304(8)nm,b=1．4158(8)sin。c=1．1417(1)nm,V=1．63801nm^3,z=4。晶体结构经块状矩阵最小二乘法修正后,最终偏离因子R=0．084。     

Bi3GaS5]2[Ga3Cl10]2[GaCl4]2·S8 containing heterocubane-type [Bi3GaS5]2+, star-shaped [Ga3Cl10]-, monomeric [GaCl4]- and crown-like S8

By reaction of elemental bismuth, sulfur, bismuth(III) chloride and gallium(III) chloride in the ionic liquid (BMIm)Cl (BMIm: 1-butyl-3-methylimidazolium), [Bi(3)GaS(5)](2)[Ga(3)Cl(10)](2)[GaCl(4)](2)·S(8) is obtained as red transparent crystals. According to X-ray structure analysis based on single crystals, the title compound crystallizes with triclinic lattice symmetry and is composed of heterocubane-type [Bi(3)GaS(5)](2+) cations, trimeric star-shaped [Ga(3)Cl(10)](-) anions with three (GaCl(4)) tetrahedra sharing a single central chlorine atom, monomeric [GaCl(4)](-) tetrahedra and neutral, crown-shaped S(8)-rings. Here, the heterocubane [Bi(3)GaS(5)](2+) as well as the star-shaped [Ga(3)Cl(10)](-) are observed as building units for the first time. [Bi(3)GaS(5)](2)[Ga(3)Cl(10)](2)[GaCl(4)](2)·S(8) is further characterized by X-ray powder diffraction as well as by thermogravimetry/differential thermal analysis.     

簇合物[Et4N]2[Mo2S4(SCH2CH2S)2]的合成及其结构研究

以(NH4)2MoS4,Et4NBr,HSCH2CH2SH为原料,合成出[Et4N]2[Mo2S4(SCH23CH2S)2]簇合物,用X射线衍射法测定了晶胞结构.其晶胞参数为a=1.0304(8)nm,b=1.4158(8)nm,c=1.1417(1)nm,V=1.63801nm3,Z=4,晶体属单斜晶系,晶体结构经块状矩阵最小二乘法修正后,最终偏离因子R=0.089.此外还进行了红外光谱,紫外可见光谱的测定.     

4[CuCl(C5H5N)4]·[W10O32]·2(C5H5N)·3H2O的合成及晶体结构

标题化合物是通过(NH_4)_2WS_4, CuCl_2·2H_2O在吡咤溶液中反应制得。晶体呈蓝色, 属三斜晶系, 空间群P1, 晶胞参数为:a=1.3555(7), b=1.3666(5), c=1.7860(13) nm, α=69.08(4)°, β=87.39(5)°, γ=70.72(4)。V=2.907(3) nm, Z=1, D_m=2.56 g cm~(-3)。结构由Patterson法和Fourier法测出。对5692个收集到的独立衍射数据进行计算, 最后R=0.046。结构测定表明, 晶体由W_(10)O_(32)~(4-), [CuCl(C_5H_5N)_4]~+, C_5H_5N和H_2O所组成。W_(10)O_(32)~(4-)的结构见图1, W原子处在O原子的八面体配位中, 彼此共边和共顶点相连。[CuCl(C_5H_5N)_4]~+的结构见图2, Cu原子由1个Cl和4个N原子配位, 呈略有变形的四方锥形, 这种离子是首次报导。C_5H_5N和H_2O填入正负离子堆积的空隙中。     

Crystal structure of Ir(III) complexes with 1,10-phenanthroline: K[Ir(phen)Cl4]·H2O and (Me4N)[Ir(phen)Cl4]

The crystal structure of two salts of the complex [Ir(phen)Cl₄]^? anion with K⁺ (K[Ir(phen)Cl₄]·H₂O, 1) and Me₄N⁺ ((Me₄N)[Ir(phen)Cl₄], 2) cations is determined. The iridium(III) ion is in a distorted octahedral environment consisting of chloride anions and a bidentate heterocyclic ligand of 1,10-phenanthroline (phen). A crucial role in the formation of the crystal structure of complex 1 belongs to K…Cl contacts, while in the crystal structure of complex 2, the stacking interactions dominate.     

[Bi2Cl10(H2-Norf)4(H2O)8](H-Norf是诺氟沙星)

CommentDuringinvestigationsonvariousmetalcomplexeswithH鄄Norf[1,2],complexationwithBiwasinvestigated.Fig.1showsthestructureofthefirstBi髥complexcontainingtheantibacterialdrugNorfloxacin○,[Bi2Cl10(H2鄄Norf)4(H2O)8].Thisisanioniccompoundcompris鄄ingfour[H2     

Formation of the ionic gold(III) complex [Au3{S2CN(CH2)4O}6][Au2Cl8][AuCl4] in chemisorption systems [M{S2CN(CH2)4O}2] n -[AuCl4]−/2 M HCl (M = Cd, Zn): Supramolecular structure and thermal behavior

The interaction of freshly precipitated cadmium and zinc morpholinedithiocarbamates with solutions of AuCl₃ in 2 M HCl is studied. In both cases, the heterogeneous reactions of gold(III) binding from solutions lead to the formation of the ionic gold(III) complex [Au₃{S₂CN(CH₂)₄O}₆][Au₂Cl₈][AuCl₄] (I), whose molecular and supramolecular structures are determined by X-ray diffraction analysis. Compound I includes centrosymmetric and noncentrosymmetric cations [Au{S₂CN(CH₂)₄O}₂]⁺ in a ratio of 1: 2. According to the manifested structural differences, the complex cations are related as conformers (cations A are Au(1) and cations B are Au(2)). At the supramolecular level, the isomeric cations form linear trinuclear structural fragments [Au₃{S₂CN(CH₂)₄O}₆]³⁺ [A...B...A] due to secondary bonds Au...S of 3.6364 Å. The anionic part of compound I is presented by [AuCl₄]^? and centrosymmetric binuclear [Au₂Cl₈]^2?, whose formation involved secondary bonds Au...Cl of 3.486 and 3.985 Å. The ultimate chemisorption capacity of cadmium and zinc morpholinedithiocarbamates calculated from the binding of gold(III) is 901.7 and 1010.4 mg of Au³⁺ per 1 g of the sorbent, respectively (i.e., each miononuclear fragment of the chemisorption complexes [M{S₂CN(CH₂)₄O}₂] participates in binding of two gold atoms). To establish the conditions for the isolation of bound gold, the thermal properties of compound I are studied by simultaneous thermal analysis. The thermal destruction process includes the thermolysis of the dithiocarbamate part of the complex and anions [AuCl₄]^? and [Au₂Cl₈]^2? with the reduction of gold to the metal, being the only final product of the thermal transformations of compound I.     

Synthesis and Crystal Structure of Two Decavanadates Cluster Metal Complexes: [Co(H2O)6]2[H2V10O28]·6H2O and (NH4)2[Ca(H2O)7]2[V10O28]

Two new decavanadate metal complexes, [Co(H₂O)₆]₂[H₂V₁₀O₂₈]·6H₂O (1) and (NH₄)₂[Ca(H₂O)₇]₂[V₁₀O₂₈] (2), have been synthesized under hydrothermal condition by using chlorhydric acid as the initiator at 120 °C. The aqueous NaVO₃ solution with an aqueous solution of CoCl₂·6H₂O were used for generating 1 and aqueous CaCl₂·2H₂O and NH₄VO₃ solution were employed for creating 2. Compound 1 consisted of discrete hexa-aqua-cobalt [Co(H₂O)₆]²⁺ cations, [H₂V₁₀O₂₈]⁴⁻ anions and non-coordination water molecules. Compound 2 were composed of hepta-aqua-calcium [Ca(H₂O)₇]²⁺ cations, ammonium NH₄ ⁺ and [V₁₀O₂₈]⁶⁻ anion. For compound 2, the distorted pentagonal bipyramid [Ca(H₂O)₇]²⁺ is uncommon. In the crystal lattice, hydrogen bonds played an important role on connecting cations, anions and non-coordinated water molecules to form the three-dimensional network.     

Crystal Structure and Superoxide Dismutase Activity of [Cu(Imidazole)2(Quinoline)Cl2]·0.5[Cu(Imidazole)4Cl2]

The preparation, spectroscopic properties and crystal structure of (bis-imidazole)quinoline-copper(II) dichloride [Cu(Im)₂(quin)Cl₂] (Im = imidazole, quin = quinoline) and tetraimidazole-copper(II)-dichloride [Cu(Im)₄Cl₂] are reported. Both cocrystallize on the triclinic system, space group P-1, with cell constants a = 8.095(5) Å, b = 12.141(5) Å, c = 13.847(5) Å, α = 108.816(5)°, β = 104.173(5)°, γ = 94.965(5)° and Z = 2. In the [Cu(Im)₂(quin)Cl₂] complex the copper(II) ion is coordinated to two imidazole molecules, to one quinoline and two chlorine ions, with the copper(II) ion in a distorted trigonal bipyramidal coordination geometry. In the [Cu(Im)₄Cl₂] complex, the copper(II) ion has a distorted octahedral coordination geometry. The superoxide dismutase mimetic activity of the complexes was investigated using the indirect xanthine-xanthine oxidase-nitroblue tetrazolium method and compared to that of the native enzyme.     

Synthesis and Structure of anti-Configuration Complex [Cu(tssb)2]·2[(H3O)Cl]·4H2O

The title complex [Cu(tssb)2]·2[(H3O)Cl]·4H2O (C18H34Cl2CuN2O14S2) (tssb = taurine salicylaldehyde Schiff base) has been synthesized by the reaction of taurine salicylaldehyde Schiff base (tssb) and copper acetate in water-ethanol. Its single-crystal structure was determined by X-ray diffraction method. The crystal structure belongs to triclinic, space group P with a = 0.7407(1), b = 1.3329(3), c = 1.5736(3)nm, α = 103.800(4), β = 95.030(4), γ = 104.416(4)°, Mr = 701.06, V = 1.4433(5) nm3, Z = 2, Dc = 1.613 g/cm3, μ = 1.153 mm-1 and F(000) = 726. The compound is an infinitely expanding three-dimensional network connected with hydrogen bonds. The Cu(Ⅱ) atom is coordinated by two nitrogen and two oxygen atoms to form a distorted planar coordination compound which adopts anti-configuration because two sulfonic acid groups are positioned diagonally on a plane.     

CLUSTER CONVERSION OF [MoW2O2(O2CEt)9]− TO [MoW2O4(O2 CEt)8]4- BY CHROMIUM HEXACARBONYL CRYSTAL STRUCTURES OF Na[MoW2O2(O2CMe)9] · H2O, [MoW2O2(O2CEt)6(H2O)3] ZnCl4 · 2H2O AND Na2Cr2[MoW2O4(O2CEt)8]2

Abstract

Reactions of Mo(CO)₆ with Na₂WO₄ · 2H₂O in refluxing carboxylic anhydride produce the triangular bioxo-capped mixed-metal carboxylate clusters Na[MoW₂O₂(O₂CR)₉] (R = Me, 1; Et, 2), the propionate being hydrolyzed in 2M HCl containing ZnCl₂ to form [MoW₂O₂(O₂CEt)⁶(H₂O)₃]ZnCl₄·2H₂O (3). Cluster 2 is converted to the incomplete cuboidal tetraanion [MoW₂O₄(O₂CEt)₈]^4- upon reacting with Cr(CO)₆ in propionic anhydride at 120°, the latter species being trapped by Cr^3± and Na^± ions in the reaction mixture to afford the octanuclear heterometallic chain-like cluster Na₂Cr₂ [MoW₂O₄(O₂CEt)₈]₂ (4). Clusters 1, 3 and 4 have been characterized by X-ray crystallography with the following crystal data, for 1: monoclinic, space group P2₁/c, a = 16.666(8), b = 11.096(3), c = 16.541(7) Å, β = 94.60(4)°, V = 3048.9 ų, Z = 4, R, Rw = 0.070, 0.079; for 3, monoclinic, space group Cm, a = 10.259(3), b = 15.756(3), c = 10.870(3) Å, β = 96.18(3)°, V = 1746.8 ų, Z = 2, R, Rw = 0.028, 0.034; for 4, triclinic, space group P-1, a = 13.013(5), b = 14.005(4), c = 12.357(4) Å, α = 109.71(2), β = 117.77(3), γ = 90.41(3)°, V = 1838.9 ų, Z = 1, R, Rw = 0.037, 0.042.     

Identification of the cobalt(II) chloride ‘mixed’ solvate Co4Cl8(H2O)4(MeCN)6: the ionic structure trans-[Co(H2O)2(MeCN)4] trans-[Co(H2O)2(MeCN)2(CoCl4)2]

The structure of the title compound features mononuclear octahedral Co^II cations, trans-[Co(H₂O)₂(MeCN)₄]²⁺, and trinuclear anions, trans-[Co(H₂O)₂(MeCN)₂(CoCl₄)₂]^2–; the latter centrosymmetric units contain a central octahedral Co(H₂O)₂(MeCN)₂ moiety with two tetrahedral [CoCl₄]^2– ligands. These two large ions are held in a network of intra- and inter-molecular hydrogen bonding.     

A novel heteropolymetalate containing Fe_4(OH)_4 segment: crystal structure of [Me_4N]_10[Fe_4(OH)_4(PW_10O_37)_2]·15H_2O

[Me4N]10[Fe4(OH)4(PW10O37)2] · 15H2O was synthesized by the reaction of FeCl3 ·6H2O, with △-Na8HPW9O34 and Me4NBr. Crystal data: M = 6225.75, space group P21/c with the monoclinic parameters: a = 1.3228(5), b = 3.5634(3), c = 1.5226(2) nm, β = 94.20(2)°, V = 7.1576nm3, 7 = 2,DC = 2.888 g/cm3, Mo Kαradiation (λ = 0.071069 nm), μ= 168.534 cm-1, F(000)=5576, final R = 0.0428 and Rw = 0.1204 for 7086 observed reflections with I > 2σ( I) . The structure of the title compound is the first structurally characterized heteropolymetalate with hydroxo-bridging metal aggregation Fe4OH4 encapsulated in the dimer of Keggin polyoxoanion.