Syntheses and Characterizations of （CH3CH2CH2CH2NH3）6（BiI6）（I）2I3 and （NH3CH2CH2NH3）2Bi2I10

The title compounds have been respectively synthesized by solution process and solvothermal reaction, and their crystal structures were determined by X-ray diffraction method. For （CH3CH2CH2CH2NH3）6（BiI6）（I）2I3 1, it crystallizes in tficlinic, space group P1^- with Mr = 2049.76, a = 8.5719（1）, b = 11.7461（3）, c = 15.700（1）A, V = 1451.4（1）A^3, Z = 1, Dc = 2.345 g/cm^3, F（000） = 924, μ（MoKα） = 8.907 mm^-1, T = 293（2） K, the final R = 0.0655 and wR = 0.0804 for 2399 observed reflections with I 〉 2σ（I）. For （NH3CH2CH2NH3）2Bi2I10 2, it crystallizes in monoclinic, space group P21/n with Mr= 1811.20, a = 8.434（4）, b = 13.862（6）, c = 13.362（6）A, V = 1499.9（12）A^3, Z = 2, Dc = 4.010 g/cm^3, F（000） = 1536,μ（MoKα） = 22.007 mm^-1, T = 293（2） K, the final R = 0.0584 and wR = 0.1451 for 1798 observed reflections with I 〉 2σ（I）. The structures of 1 and 2 contain halobismuthate monomer and dimers, respectively. It is noteworthy that the dimers and their organic counters in 2 connect each other by N…I hydrogen bonds to form a layered structure, and the electrostatic interactions and crystal packing forces between layers give rise to the packing of the crystal. The optical absorption spectra of 1 and 2 reveal the appearance of sharp optical gaps of 2.13 and 2.01 eV, respectively.     

Synthesis and Crystal Structure of an Incomplete Cubane-type Mo3S4 Cluster with the N-N-O Type Tridentate Ligand：[Mo3S4[NH2CH2CH（O）CH2NH2]3}（DTP）- （H2O）2- （DMF）

1 INTRODUCTION It is of significance to investigate the reactivity of trinuclear molybdenum sulfide cluster compounds for their interesting chemistry and potential applica- tions on catalysis[1, 2]. The earlier researches estab- lished that Mo3S4(DTP)4(H2O) has three ligand substitution sites: the loosely-coordinated ligand H2O, the bridging DTP and the terminal DTP ligands. Among these three reaction sites, the reac- tivity follows the sequence of H2O > b-DTP > t-DTP. The loose…     

Mo—Cu—S原子簇化合物[Mo2Cu6S6（SCMe3）2（O）2（PPh3）4]（Ⅰ）和[MoCu3S3（S2COEt）

基于标题簇合物的快原子质谱研究，提出该二簇合物在质谱过程中的可能断裂途径及其簇骼转换的相关性。     

Synthesis and Structure of [HOCH2CH2N（CH3）3]4[Cu4OCl10]

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Synthesis and Characterization of [NH3（CH2）2NH2（CH2）2NH3]BiCl6

1 INTRODUCTION During the past decade, a series of organic-inor- ganic hybrid compounds based on metal halide units have been prepared and studied[1]. The combination of organic and inorganic components at the mole- cular level affords us the opportunity to design new hybrid materials and modulate the properties of components[2]. As a result, some interesting proper- ties, such as non-linear optical[3], interesting magne- tic[4], efficient luminescence[2], ideal thermal and mechanical sta…     

Solvothermal Synthesis and Crystal Structure of [H2N（CH2）2NH3]{Co[H2N（CH2）2NH2]3}[SbSe4]

1 INTRODUCTION The chalcogenidometallates with open frame- works have attracted considerable interest as pos- sible zeolite-like materials, of which highly interes- ting properties could be expected. Over the last de- cades a large number of thioanti…     

Synthesis, Structure Characterization and Biological Activity of Layered Vanadium Oxides [ NH3 （ CH2 ）2 NH （ CH2 ）2 NH3 ] [ V6 O14 ]

Introduction Over the past decades, polyoxometalates(POMs)have been attracting extensive interestowing to the widerange of their topological properties and potential appli-cations in catalysis, photochemistry, electrochromism,and magnetism[1,2]. Meanwhile, owing to the potentialapplication of polyoxometalaes as anticancer and antivi-ral drugs, their complexes have attracted increasing in-terest of both inorganic chemists and biochemists[3]. Itis well known that polyoxometalates are excellent …     

Synthese und Kristallstrukturen von (PPh4)2[TeS3] · 2 CH3CN und (PPh4)2[Te(S5)2]

Synthesis and Crystal Structures of (PPh₄)₂[TeS₃] · 2 CH₃CN and (PPh₄)₂[Te(S₅)₂] (PPh₄)₂[TeS₃] · 2 CH₃CN was obtained by the reaction of PPh₄Cl, Na₂S₄ and Te in acetonitrile. With sulfur it reacts yielding (PPh₄)₂[Te(S₅)₂]. The crystal structures of both products were determined by X-ray diffraction. (PPh₄)₂[TeS₃] · 2 CH₃CN: triclinic, space group P1 , Z = 2, R = 0.041 for 4 629 reflexions; it contains trigonal-pyramidal [TeS₃]^2? ions with an average Te? S bond length of 233 pm. (PPh₃)₂[Te(S₅)₂]: monoclinic, P2₁/n, Z = 2, R = 0.037 for 2 341 reflexions. In the [Te(S₅)₂]^2? ion the tellurium atom has a nearly square coordination by four S atoms. Along with the Te atoms each of the two S₅ groups forms a ring with chair conformation.     

Synthesis and structure of an open-type trinuclear molybdenum cluster compound[Mo_3(μ_3-S)(μ-S)_2-(μ-OAc)(S_2CNC_4H_8)_3(O)_2]·0.5CH_2Cl_2·2H_2O

The title compound was prepared by the reaction of Mo_3S_4(dtp)_4(H_2O)[ctp=S_2P(OEt)_2]with NaOAc·3H_2O and C_4H_8NCS_2NH_4.Crystallographic data:[Mo_3(μ_3-S)(μ-S)_2(μ-OAc)-(S_2CNC_4H_8)_3(O)_2]·0.5CH_2CI_2·2H_2O,Mr=980.18,triclinic,space group P,α=12.360(3),b=16.653(6),c=9.206(2)A,α=101.97(2),β=108.32(2),γ=86.14(3)°.V=1759.6(9)A~3,Z=2,Dc=1.85 g/cm~3,F(000)=962,μ(Mo K_α)=16.53 cm~(-1).Final R=0.044 for 4301 reflections with I≥3σ(I).This compoundmay be regarded as a mixed-valent trinuclear molybdenum cluster{Mo_2(V)Mo(Ⅳ)(μ_3-S)(μ-S)_2-(μ-OAc)(S_2CNC_4H_8)_3(O)_2}.The Mo-Mo distances are 2.783(1),2.833(1)and 3.374(2)A in the Mo_3non-equilateral triangle and there exist only two Mo-Mo bonds.The cluster was obtained by oxi-dation and ligand substitution of{Mo_3(μ_3-S)(μ-S)_3[μ-S_2P(OEt_2)][S_2P(OEt)_2]_3(H_2O)}.     

Kristallstruktur und Schwingungsspektrum von (H2NPPh3)2[SnCl6]·2CH3CN

Crystal Structure and Vibrational Spectrum of (H₂NPPh₃)₂[SnCl₆]·2CH₃CN Single crystals of (H₂NPPh₃)₂[SnCl₆]·2CH₃CN ( 1 ) were obtained by oxidative addition of tin(II) chloride with N‐chloro‐triphenylphosphanimine in acetonitrile in the presence of water. 1 is characterized by IR and Raman spectroscopy as well as by a single crystal structure determination: Space group , Z = 2, lattice dimensions at 193 K: a = 1029.6(1), b = 1441.0(2), c = 1446.1(2) pm, α = 90.91(1)°, β = 92.21(1)°, γ = 92.98(1)°, R₁ = 0.0332. 1 forms an ionic structure with two different site positions of the [SnCl₆]^2? ions. One of them is surrounded by four N‐hydrogen atoms of four (H₂NPPh₃)⁺ ions, four CH₃CN molecules form N–H···N≡C–CH₃ contacts with the other four N‐hydrogen atoms of the cations. Thus, 1 can be written as [(H₂NPPh₃)₄(CH₃CN)₄(SnCl₆)]²⁺[SnCl₆]^2?.     

Synthesis and Characterization of Ethylenediammonium Molybdenum Thiocomplex [H3NCH2CH2NH3][Mo3S13]

An organo‐spaced molybdenum thiocomplex [ H₃NCH₂CH₂‐NH₃][Mo₃S₁₃] has been synthesized under hydrothermal condition and the structure of the compound was determined by single‐crystal X‐ray diffraction. The title compound crystallizes in the monoclinic space group C2/c with a = 1.81157 (18), b = 1.04549(9), c = 2.04892(19) nm, β= 107.184 (2)°, Z = 8 and V = 3.7074(6) nm³. The inorganic part of the compound consists of a Mo₃ triangle capped by an apical μ₃‐sulfur atom, with each Mo atom being also coordinated to one terminal disulfur ligand and two bridging disulfur ligands. The negative charges on the inorganic cluster are balanced by the diprotonated ethylenediamine cations [ H₃NCH₂CH₂‐NH₃]²⁺ located in the space between the clusters.     

Darstellung und Reaktionen von Natriumtellurid,Na2Te – Kristallstruktur von [Na(CH3OH)3]2Te2

Preparation and Reactions of Sodium Telluride, Na₂Te – Crystal Structure of [Na(CH₃OH)₃]₂Te₂ Sodium telluride, Na₂Te 1 , is easily obtained by reaction of sodium with hexagonal tellurium in 1,2-dimethoxy-ethane in the presence of catalytic amounts of naphthalene. Upon exposure to oxygen 1 reacts with methanol forming [Na(CH₃OH)₃]₂Te₂ 2 , which crystal structure was determined. Compound 1 , prepared in situ, can be conveniently converted into dialkyl tellurides, R₂Te (R = C₂H₅, i-C₃H₇, CH₂ = CH? CH₂ 3 ).     

Darstellung und Kristallstruktur der Addukte [DB-18C6] · CH3CN · CH3CSOH und [DC-18C6](CH3CSOH)2 sowie der salzartigen Verbindungen [Cs(B-15C5)2]CH3CSS und [Cs(DB-18C6)]2S5(DMF)21)

Synthesis and Crystal Structure of the Adducts [DB-18C6] · CH₃CN · CH₃CSOH and [DC-18C6](CH₃CSOH)₂ as well as of the Salt-like Compounds [Cs(B-15C5)₂]CH₃CSS and [Cs(DB-18C6)]₂S₅(DMF)₂¹) The reaction products of crown ethers, cesium, and sulfur in aprotic solvents like acetonitrile and dimethylformamide strongly depend on the reaction conditions. Using CH₃CN as a solvent, sometimes neutral host-guest adducts crystallize only, e.g., [dibenzo-18C6] · CH₃CN · CH₃CSOH (monoclinic, S. G. P2₁/c, Z = 4, a = 9.73(1) Å, b = 22.03(1) Å, c = 11.86(1) Å, β = 91.8(1)°) or [dicyclohexyl-18C6](CH₃CSOH)₂ (monoclinic, S. G. P2₁/n, Z = 2, a = 7.75(1) Å, b = 10.32(1) Å, c = 17.73(1) Å, β = 95.7(1)°). The monothioacetic acid, CH₃CSOH, must be regarded as the first product of the hydrolysis of CH₃CN. Furthermore, another product of this kind of hydrolysis, CH₃CSSH, is obtained too. Therefore, we also obtain the salt-like compound [Cs(benzo-15C5)₂]CH₃CSS (monoclinic, S. G. C2/c, Z = 4, a = 16.05(1) Å, b = 16.73(1) Å, c = 13.11(1) Å, β = 106.3(1)°). If the solvent DMF is used, the pentasulfide [Cs(dibenzo-18C6)]₂S₅(DMF)₂ crystallizes (monoclinic, S. G. P2₁/n, Z = 4, a = 14.79(1) Å, b = 14.24(1) Å, c = 25.74(1) Å, β = 92.7(1°. The S₅^2? anions show the cis-conformation.     

Synthesis and Crystal Structure of a Decanuclear Silver（I）-thiolate Compound Ag10S[S2P（OEt）2]8

A new decanuclear silver(I) compound Ag₁₀(μ₈‐S)(dtp)₈ [dtp=S₂P(OEt)₂] was isolated from a reaction mixture containing W₂S₄(dtp)₂ and AgN0₃, and its solid‐state molecular structure was determinated by X‐ray crystallography. The crystallographic study revealed that the compound contains a distorted mono‐capped quasi‐prism [Ag_io] with an octat‐bridging S atom at the center of the prism. The compound (C₃₂H₈₀Ag₁₀O₁₆P₈S₁₇, M_r=2592.46) crystallizes in the monoclinic P2₁/n space group, with a = 1.5111(5) nm, b=2.3656(8) nm, c=2.284(1) nm, β= 96.88(3)°, V=8.107(5) nm³, Z=4 and D,=2.12 g · cm^?3. The solution using direct method and full‐matrix least‐squares refinement led to R=0.066, Rw=0.078 for 3928 reflections with I3σ(I).     

Synthese und Kristallstruktur von (PPh4)2[Mo2(S2)2Cl8] · 2 CH3CN und seine topotaktische Umwandlung zu (PPh4)2[Mo2(S2)2Cl8]

Synthesis and Crystal Structure of (PPh₄)₂[Mo₂(S₂)₂Cl₈] · 2 CH₃CN and its Topotactic Transformation to (PPh₄)₂[Mo₂(S₂)₂Cl₈] MoS₂Cl₃ was prepared from molybdenum and S₂Cl₂ at 200 °C. Its reaction with PPh₄Cl in acetonitrile yielded (PPh₄)₂[Mo₂(S₂)₂Cl₈] · 2 CH₃CN. In vacuum or upon warming, it loses the acetronitrile without degradation of the crystals. According to the X-ray crystal structure determinations both compounds, with and without acetonitrile, are triclinic. They contain the same [Cl₄Mo(μ-S₂)₂MoCl₄]^2– ions, in which the Mo atoms are joined by two disulfido groups and an Mo–Mo bond. Details of the crystal packings and their topotactic transformation are given.     

Reactions of M3Te7 (M = Mo, W) clusters with electrophilic reagents: Chalcogen exchange in the Te2 ligand and the first complexes of (TeS)

Reactions of triangular telluride-bridged Mo and W clusters [M₃(μ₃-Te)(μ₂-Te₂)₃(dtp)₃]⁺ (M = Mo, W; dtp = (EtO)₂PS₂) with S₂Cl₂ or Br₂ lead to Te/S exchange in the Te₂ ligands, with the formation of complexes with a novel TeS²⁻ ligand. Reaction of [W₃(μ₃-Te)(μ₂-Te₂)₃(dtp)₃]⁺ with Br₂ or S₂Cl₂ gives a mixture of complexes formulated as [W₃Te_4.25S_2.75(dtp)₃]⁺ and [W₃Te_4.30S_2.70(dtp)₃]⁺, respectively, on the basis of X-ray structural analysis. Reaction of the Mo homolog, namely [Mo₃(μ₃-Te)(μ₂-Te₂)₃(dtp)₃]⁺, with S₂Cl₂ gives rise to [Мо₃Te_4.74S_2.26((EtO)₂PS₂)₃]⁺. Electrospray ionization mass spectrometry (ESI-MS) complements the information gathered from X-ray analysis regarding the degree of Te by S substitution; moreover, detailed insights on the regioselectivity of such replacement are also obtained from ESI-MS analysis. These experimental evidences indicate that Te by S replacement in W complexes display high regioselectivity (as evidenced by the exclusive formation of a W₃Te₄S₃⁴⁺ core), the equatorial Te ligands being preferentially replaced over the Te_ax and μ₃-Te ligands. Conversely, for the Mo homologs, a broad distribution of Mo₃Te_7−xS_x⁴⁺ cluster species ranging from x = 0 to 6 is observed. Bond distance analysis as well as crystal packing trends as a function of the cluster core M₃Te_7−xS_x⁴⁺ (M = Mo, W; x = 0–6) composition are also reported.     

The reactivities of Mo cluster — A selective substitution reaction of the bridging (dtp) ligand and the crystal structure of {Mo3S4(μ-O2CR)(dtp)3(Py)}

The reaction of trinuclear molybdenum cluster {Mo₃S₄(μ-dtp) (dtp)₃ (H₂O)} 1 [dtp= S₂P(OEt)₂] with RCO₂Na (R?H, CH₃) in the presence of Py gave the black compounds {Mo₃S₄ {μ-O₂ CR) (dtp)₃ (Py)} (2, R?H, 3, R?CH₃). Both compounds are characterized by X-ray crystallography. It is shown that crystals 2 and 3 belong to space group P&1bar; with Z=2 and a=10.519(2), b= 12.121(2), c=15.757(2)Å, α=93.27(1), β=94.63(1), γ = 105.22(1)°, V= 1925 ų for crystal 2, whereas a=9.556 (2), b=14.067(7), c=15.914 (9) Å, α=101.41 (4), β=101.44(4), γ-74.26(3)°, V=1994ų for crystal 3. The final R factors are 0.041 and 0.048 for crystal 2 and 3 respectively. The structure analysis indicates that (O₂CR)^? ligand selectively substitutes the bridging (dtp) ligand. This type of Mo, cluster molecule where structure contains two species of bidentate ligand is for the first time to be obtained by us.