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Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O], and (PPh4)2[SnCl6] · S8 · 2CH3CN . The reaction of PPh4[SnCl3] with Na2S4 in acetonitrile in the presence of small amounts of water yields (PPh4)2[Sn4Cl4S5(S3)O] and minor amounts of (PPh4)2[SnCl2(S6)2], PPh4Cl · 2S8 and (PPh4)2[SnCl6]. SnCl4 is partially reduced by (PPh4)2Sx, PPh4[SnCl3] and (PPh4)2[SnCl6] · S8 · 2CH3CN being produced. According to the X-ray crystal structure determination the [Sn4Cl4S5(S3)O]2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S3 group. In the [SnCl2(S6)2]2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S6 groups. Octahedral [SnCl6]2? ions and S8 molecules in the crown conformation are present in (PPh4)4[SnCl6] · S8 · 2CH3CN. 相似文献
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Synthesis and Crystal Structures of (PPh4)2[In(S4)(S6)Cl] and (PPh4)2[In(S4)Cl3] InCl and PPh4Cl yield (PPh4)2[In2Cl6] in acetonitrile. This reacts with Na2S4 in presence of PPh4Cl, forming (PPh4)2[In(S4)(S6)Cl]. Its crystal structure was determined by X-ray diffraction (R = 0.075, 2 282 observed reflexions). It is isotypic with (PPh4)2[In(S4)(S6)Br] and contains anions with trigonal-bipyramidal coordination of In, Cl occupying an axial position, and the S4 and S6 groups being bonded in a chelate manner. The reaction of (PPh4)2[In2Cl6] and sulfur in acetonitrile yielded (PPh4)2[InCl5] and (PPh4)2[In(S4)Cl3]. The crystal structure analysis of the latter (R = 0.072, 4 080 reflexions) revealed an anion with distorted trigonal-bipyramidal coordination of In, the S4 group occupying one axial and one equatorial position; the S4 group shows positional disorder. 相似文献
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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. 相似文献
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Formation of PPh4[WOCl4 · THF] and PPh4Cl · 4As4S3 from W(CO)6 and PPh4[As2SCl5] and their Crystal Structures When W(CO)6 and PPh4[As2SCl5] are irradiated with UV light in tetrahydrofurane, PPh4[WOCl4 · THF], PPh4 Cl· 4As4S3 and PPh4[Cl2H] are obtained. X-ray crystal structure determinations were performed. PPh4[WOCl4 · THF], monoclinic, space group P21/c, Z = 4, a = 1207.5(2), b = 1003.7(2), c = 2642.0(5) pm, β = 114.71(1)°, R = 0.049% for 2824 reflexions; PPh4+ and [WOCl4. THF]? ions are present, the WOCl4 group having the shape of a tetragonal Pyramid with a short W ? O bond (169 pm) and the THF molecule being weakly associated (W? O 236 pm). PPh4Cl · 4AsS3, tetragonal, I41/a, Z = 4, a = 1742.3(3), c = 1664.5(4) pm, R = 0.066% for 1350 reflexions; it consists of separate PPh4+ and Cl? ions and As4S3 molecules. 相似文献
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Syntheses and Crystal Structures of Chalcogenido‐bridged Nickel Cluster Compounds [Ni5Se4Cl2(PPhEt2)6], [Ni12Se12(PnPr3)6], and [Ni18S18(PiPr3)6] The reaction of (R)ESiMe3 (R = SiMe3, Mes = C9H11; E = S, Se) with [NiCl2(PPhEt2)2] and [NiCl2(PR3)2] (R = nPr, iPr) gives new chalcogenido‐bridged nickel cluster compounds [Ni5Se4Cl2(PPhEt2)6]·2THF ( 1 ), [Ni12Se12(PnPr3)6]·2THF ( 2 ), and [Ni18S18(PiPr3)6]·2THF ( 3 ). The structures of these compounds were determined by single crystal X‐ray structural analyses. 相似文献
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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. 相似文献
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Syntheses and Crystal Structures of [Pd9As8(PPh2)8] and [Pd9Sb6(PPh3)8] [PdCl2(PPh3)2] reacts with As(SiMe3)3 to give the new cluster [Pd9As8(PPh3)8] ( 4 ). 4 has been characterized by X-ray crystal structure analysis. It is a molecule in which four [Pd2(PPh3)2]-units are bridged by As2-units. A further Pd atom is located in the centre of the cluster. 4 crystallizes in the space group C2/c with four formula units per unit cell. The lattice constants at 200 K are: a = 3 970.6(3), b = 1 648.90(16), c = 3 266.30(20) pm, β = 131,44(4)°. The reaction of [PdCl2(PPh3)2] with Sb(SiMe3)3 yields [Pd9Sb6(PPh3)8] ( 5 ). 5 consists of a body centred cubic Pd9-cluster. All of the cube faces are capped by μ4-Sb-ligands. 5 crystallizes in the space group Pn3 with two formula units per unit cell. The lattice constants at 200 K are: a = b = c = 1 995.4(2) pm. 相似文献
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Reactions of Uranium Pentabromide. Crystal Structures of PPh4[UBr6], PPh4[UBr6] · 2CCl4, (PPh4)2[UBr6] · 4CH3CN, and (PPh4)2[UO2Br4] · 2CH2Cl2 PPh4[UBr6] and PPh4[UBr6] · 2CCl4 were obtained from UBr5 · CH3CN and tetraphenylphosphonium bromide in dichloromethane, the latter being precipitated by CCl4. Their crystal structures were determined by X-ray diffraction. PPh4[UBr6]: 2101 observed reflexions, R = 0.090, space group C2/c, Z = 4, a = 2315.5, b = 695.0, c = 1805.2 pm, β = 96.38°. PPh4[UBr6] · 2CCl4: 2973 reflexions, R = 0.074, space group P21/c, Z = 4, a = 1111.5, b = 2114.2, c = 1718.7 pm, β = 95.42°. Hydrogen sulfide reduces uranium pentabromide to uranium tetrabromide. Upon evaporation, bromide is evolved from solutions of UBr5 with 1 or more then 3 mol equivalents of acetonitrile in dichlormethane yielding UBr4 · CH3CN and UBr4 · 3CH3CN, respectively. These react with PPh4Br in acetonitrile affording (PPh4)2[UBr6] · 4CH3CN, the crystal structure of which was determined: 2663 reflexions, R = 0.050, space group P21/c, Z = 2, a = 981.8, b = 2010.1, c = 1549.3 pm, β = 98.79°. By reduction of uranium pentabromide with tetraethylammonium hydrogen sulfide in dichloromethane (NEt4)2[U2Br10] was obtained; (PPh4)2[U2Br10] formed from UBr4 and PPh4Br in CH2Cl2. Both compounds are extremely sensitive towards moisture and oxygen. The crystal structure of the oxydation product of the latter compound, (PPh4)2[U02Br4]· 2 CH2Cl2, was determined: 2163 reflexions, R = 0.083, space group C2/c, Z = 4, a = 2006.3, b = 1320.6, c = 2042,5 pm, β = 98.78°. Mean values for the UBr bond lengths in the octahedral anions are 266.2 pm for UBr6-, 276.7 pm for UBr62? and 282.5 pm for UO2Br42? 相似文献
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Syntheses and Crystal Structures of the Thiochloroantimonates(III) PPh4[Sb2SCl5] and (PPh4)2[Sb2SCl6]. CH3CN (PPh4)2Sb3Cl11, obtained from Sb2S3, PPh4Cl and HCl, reacts with Na2S4 in acetonitrile forming PPh4[Sb2SCl5]. From this and Na2S4 or from (PPh4)2[Sb2Cl8] and Na2S4 or K2S5 in acetonitrile (PPh4)2[Sb2SCl6] · CH3CN is obtained. Data obtained from the X-ray crystal structure determinations are: PPh4[Sb2SCl5], monoclinic, space group P21/c, a = 1002.9(3), b = 1705.6(5), c = 1653.7(5) pm, β = 99.12(2)°, Z = 4, R = 0.068 for 1283 reflextions; (PPh4)2[Sb2SCl6] · CH3CN, triclinic, space group P1 , a = 1287.8(7), b = 1343.6(9), c = 1696.5(9) pm, α = 69.82(5), β = 85.08(4), γ = 71.54(6)°, Z = 2, R = 0.059 for 6409 reflexions. In every anion two Sb atoms are linked via one sulfur and one ore two chloro atoms, respectively. Paris of [SbSCl5]? ions are associated via Sb …? S and Sb …? Cl contacts forming dimer units. In both compounds every Sb atom has a distorted octahedral coordination when the lone electron pair is included in the counting. 相似文献
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PPh4[As3S3Cl4] and PPh4[As3S3Br4] When As2S3 reacts with PPh4X and HX in 1,2-C2H4X2 (X = Cl, Br), the title compounds are obtained as minor products; the main products are PPh4[As2SX5]. Their crystal structures were determined by X-ray diffraction. PPh4[As3S3Cl4]: a = 1187.7, b = 1090.9, c = 1191.8 pm, α = 82.91, β = 88,93, γ = 88.52°; twins with twin plane (100); R = 0.109 for 1618 observed reflexions of one twin crystal. PPh4[As3S3Br4]: a = 1119.7, b = 1177.5, c = 1204.1 pm, α = 81.59, β = 85.88, γ = 88.25°; R = 0.061 for 2331 observed reflexions. Both compounds crystallize in the space group P1 , Z = 2, and can be considered to be isotypic. Nevertheless, PPh4[As3S3Br4] does not form twins as PPh4[As3S3Cl4]. The crystals consist of PPh4+ and [As3S3X4]? ions. In the anions, the three As atoms of an As3S3 ring in the chair conformation are commonly joined to an X atom and each As atom is bonded to one further terminal X atom. Cations and anions are packed in alternating layers. 相似文献
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Thiochloroarsenates (III): Preparation, Vibrational Spectra, and Crystal Structures of PPh4[As2SCl5] and (PPh4)2[As2SCl6] · C2H4Cl2 PPh4[As2SCl5] can be obtained from As2S3 + PPh4Cl with HCl in CH2Cl2 or 1,2-C2H4Cl2. It reacts with a second mole of PPh4Cl to yield (PPh4)2[As2SCl6]. The latter also is formed by the reaction of As2S5 + 2 PPh4Cl with HCl, a second product being (PPh4)2[As2Cl8]. The i.r. and Raman spectra of the title compounds are reported. Their crystal structures were determined by X-ray diffraction. Crystal data: PPh4[As2SCl5], monoclinic, space group P21/n, a = 1175.8, b = 1508.0, c = 1593.4 pm, β = 96.22°, Z = 4; (PPh4)2[As2SCl6] · C2H4Cl2, triclinic, P1, a = 1166.3, b = 1188.2, c = 2044.6 pm, α = 95.47, β = 97.53, γ = 111.05°, Z = 2. Including the lone electron pairs, the coordination of the As atoms in the [As2SCl5]− ion is distorted trigonal-bipyramidal with the S, one Cl atom, and an electron pair in equatorial positions; the two bipyramids around the two As atoms share a common edge. The As atoms in the [As2SCl6]2− ion have a distorted octahedral coordination, the two octahedra share a common face; the lone electron pairs are in the trans positions to the S atom. 相似文献
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Syntheses and Crystal Structures of new Amido- und Imidobridged Cobalt Clusters: [Li(THF)2]3[Co3(μ2-NHMes)3Cl6] (1), [Li(DME)3]2[Co18(μ4-NPh)3(μ3-NPh)12Cl3] (2), [Li(DME)3]2[Co6(μ4-NPh)(μ2-NPh)6(PPh2Et)2] (3), and [Li(THF)4][Co8(μ3-NPh)6(μ2-NPh)3(PPh3)2] (4) The reactions of cobalt(II)-chloride with the lithium-amides LiNHMes and Li2NPh leads to an amido-bridged multinuclear complex [Li(THF)2]3[Co3(μ2-NHMes)3Cl6] ( 1 ) as well as to the imido-bridged cobalt cluster [Li(DME)3]2[Co18(μ4-NPh)3(μ3-NPh)12Cl3] ( 2 ). In the presence of tertiary phosphines two imido-bridged cobalt clusters [Li(DME)3]2[Co6(μ4-NPh)(μ2-NPh)6(PPh2Et)2] ( 3 ) and [Li(THF)4][Co8(μ3-NPh)6(μ2-NPh)3(PPh3)2] ( 4 ) result. The structures of 1 – 4 were characterized by X-ray single crystal structure analysis. 相似文献
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(PPh4)2[V2Cl9][VCl5] · CH2Cl2. Synthesis, I.R. Spectrum, and Crystal Structure The title compound was obtained by addition of CCl4 to a solution of PPh4Cl and excess VCl4 in CH2Cl2. It forms black crystals which are light and moisture sensitive. The i.r. spectrum is reported. The crystal structure was determined by X-ray diffraction (3044 independent reflexions, R = 0.063). Crystal data: triclinic, space group P1 , Z = 2, a = 1186, b 1325, c = 1995 pm, α 97.5, β 105.6°, γ 93.4°. The structure consists of PPh4+ cations, V2Cl9? and VCl5? anions and CH2Cl2 molecules. The V2Cl9? ions consist of face-sharing octahedra with a long V…?V distance of 333 pm; the VCl5? ions form nearly ideal trigonal bipyramids with V? Cl bonds of 228 pm (axial) and 218 pm (equatorial). Both anions deviate only marginally from D3h symmetry. Half of the cations is arranged to (PPh4+)2 pairs about inversion centers. 相似文献
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(PPh4)2[WO2Cl3]2 · 2 CH2Cl2. Synthesis, Vibrational Spectrum, and Crystal Structure Depending on the stoichiometry and the solvent, dichloromethane or 1.2-dichloroethane, WO2Cl2 reacts with tetraphenylphosphonium chloride affording (PPh4)2[WO2Cl4] or (PPh4)2[WO2Cl3]2, respectively. Both compounds are easily soluble in dichloromethane, from which they can be crystallized under incorporation of two molecules CH2Cl2 per formula unit. The crystalline compounds have been characterized by their IR and Raman spectra. According to the X-ray crystal structure analysis, (PPh4)2[WO2Cl3]2 · 2 CH2Cl2 crystallizes in the triclinic space group P1 with one formula unit per unit cell (986 independent observed reflexions, R = 0.061). Lattice constants: a = 1100.2, b = 1116.9, c = 1238.4 pm, = 69.40, = 80.46 and = 85.62°. The crystals consist of PPh4⊕ ions, centrosymmetric [WO2Cl3]22? anions and CH2Cl2 molecules. In the anions, the tungsten atoms are linked via two oxo bridges with WO distances of 184 and 252 pm. The distorted octahedral coordination around each tungsten atom is completed by three terminal chloro and one terminal oxo ligand (WO bond length 166 pm), the latter being in trans position to the longer WO bridging bond. (PPh4)2[WO2Cl4] · 2 CH2Cl2 also forms triclinic crystals that are isotypic with (PPh4)2[WOCl5] · 2 CH2Cl2 and in which the anions must have orientational disorder. 相似文献
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