Neue Synthesewege für Thiohalogeno- und Cyclothioarsenate(III). Kristallstrukturen von PPh4[As2SBr6] · CH3CN und PPh4[SAsS5]

Novel Routes to the Synthesis of Thiohalogeno- and Cyclothioarsenates(III). Crystal Structures of PPh₄[As₂SBr₆] · CH₃CN and PPh₄[SAsS₅] By reactions of (PPh₄)₂[As₂Cl₈] and (PPh₄)₂[As₂Br₈] with Na₂S₄ in acetonitrile (PPh₄)₂[As₂SCl₆] · CH₃CN and (PPh₄)₂[As₂SBr₆] · CH₃CN were obtained, respectively. Using K₂S₅, PPh₄[As₂SCl₅] and PPh₄[SAsS₅] were the products. The latter can also be obtained from PPh₄[As₂SCl₅] and Na₂S₄, while PPh₄[As₃S₃Br₄] is formed from PPh₄[As₂SBr₅] with K₂S₅. Two X-ray crystal structure determinations were performed. PPh₄[As₂SBr₆] · CH₃CN: triclinic, P1 , Z = 2, a = 1200.4(7), b = 1507.3(6), c = 1594.4(8) pm, α = 81.59(2), β = 78.22(3), γ = 80.58(2)°, R = 0.096 for 2298 observed reflexions. The structure contains [As₂SBr₆]^2? -ions in which the two Sb atoms are joined via one S and two Br atoms. PPh₄[SAsS₅]: triclinic, P1 , Z = 2, a = 1133.9(4), b = 1142.5(4), c = 1186.9(5) pm, α = 102.77(4), β = 107.74(3), γ = 106.65(3)°, R = 0.043 für 2677 reflexions. In the [SAsS₅]^? -ion an AsS₅ ring in the chair conformation is present.     

Tetraphenylphosphonium-tetraiodotrithiotriarsenat,PPh4[As3S3I4]

Tetraphenylphosphonium tetraiodotrithiotriarsenate, PPh₄[As₃S₃I₄] PPh₄[As₃S₃I₄] is formed along with PPh₄I₃ and other unidentified compounds by the reaction of As₂S₃, PPh₄I and HI in CH₂I₂ at 80°C. PPh₄[As₃S₃I₄] was characterized by its IR spectrum and an X-ray crystal structure determination (3684 unique observed reflexions, R = 0.083). Crystal data: a = 1390.3, b = 1548.9, c = 1505.4 pm, β = 91.08°, monoclinic, P2₁/c, Z = 4. The crystals are not isotypic with the corresponding chloro and bromo compounds, although the anion constitutions are of the same type. The [As₃S₃I₄]^? ion consists of an As₃S₃ ring in the chair conformation, the three As atoms are commonly linked to a bridging I atom and each As atom is bonded to one terminal I atom. Cations and anions are packed in alternating layers.     

Die Bildung von PPh4[WOCl4 · THF] und PPh4Cl · 4As4S3 aus W(CO)6 und PPh4[As2SCl5] sowie ihre Kristallstrukturen

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.     

Pentabromothio-diarsenat und -diantimonat: Darstellung,Schwingungsspektren und Kristallstrukturen von PPh4[As2SBr5] und PPh4[Sb2SBr5]

Pentabromothio-diarsenate and -diantimonate: Preparation, Vibrational Spectra, and Crystal Structures of PPh₄[As₂SBr₅] and PPh₄[Sb₂SBr₅] The title compounds were obtained in CH₂Br₂ from PPh₄Br, HBr and As₂S₃ or Sb₂S₃, respectively. Their i.r. and Raman spectra are reported. Their crystal structures were determined by X-ray diffraction. Crystal data: PPh₄[As₂SBr₅], monoclinic, space group P2₁/n, Z = 4, a = 1192.3, b = 1528.1, c = 1618.0 pm, β = 95.53°, isotypic with PPh₄[As₂SCl₅] (structure determination with 1539 observed reflexions, R = 0.052); PPh₄[Sb₂SBr₅], triclinic, space group P1 , Z = 2, a = 1044,8, b = 1207.1, c = 1307.8 pm, α = 104.77, β = 108.63, γ = 98.34° (2398 observed reflexions, R = 0.032). Both ions, [As₂SBr₅]^? and [Sb₂SBr₅]^?, have the same general structure: including the lone electron pairs, the As and Sb atoms have distorted trigonal-bipyrimidal coordination, two bipyramids sharing a common edge with sulfur and bromine as bridging atoms. The [As₂SBr₅]^? ions are associated to chains via As…Br contacts, the [Sb₂SBr₅]^? ions form pseudodimeric units by Sb…S and Sb…Br contacts. Whereas the crystal packing of the As compound is similar to that of other PPh₄⁺ compounds having a cation to anion ratio of 1:1, the Sb compound shows the packing principle known for 2:1 compounds.     

Thiochloroarsenate(III): Darstellung,Schwingungsspektren und Kristallstrukturen von PPh4[As2SCl5] und (PPh4)2[As2SCl6] · C2H4Cl2

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.     

Thiobromokomplexe von Arsen und Antimon Darstellung und Kristallstrukturen von (PPh4)2[As2SBr6] · CH2Br2 und (PPh4)2[Sb2SBr6] · CH2Br2

Thiobromo Complexes of Arsenic and Antimony. Preparation and Crystal Structures of (PPh₄)₂[As₂SBr₆] · CH₂Br₂ and (PPh₄)₂[Sb₂SBr₆] · CH₂Br₂ (PPh₄)₂[As₂SBr₆] · CH₂Br₂ is formed by the reaction of As₂S₃, PPh₄I and HI in dibromomethane. It can also be obtained, as well as (PPh₄)₂[Sb₂SBr₆] · CH₂Br₂, from (PPh₄)₂[As₂Br₈] and (PPh₄)₃[Sb₂Br₉], respectively, with bistrimethylsilylsulfide. The crystal structures of the title compounds were determined by X-ray diffraction. They are isotypic with (PPh₄)₂[As₂SCl₆] · C₂H₄Cl₂. In the anions [M₂SBr₆]^2? the M atoms (As or Sb) have a distorted octahedral coordination, the two octahedra share acommon face with one bridging S and two Br atoms; the lone electron pairs occupy the trans positions to the S atom. Crystal data: triclinic, space group P1 , Z = 2; (PPh₄)₂[As₂SBr₆] · CH₂Br₂, a = 119.1, b = 1203.6, c = 2067.5 pm α= 94.89, β = 97.78, γ = 112.20°, 3046 independent observed reflexions, R = 0.083; (PPh₄)₂[Sb₂SBr₆] · CH₂Br₂, a = 1198.9, b = 1224.3, c = 2085.5pm, α = 95.04, β = 98.48, γ = 112.13°C, 2380 reflexions, R = 0.079.     

Synthese und Kristallstrukturen der Thiochloroantimonate(III) PPh4[Sb2SCl5] und (PPh4)2[Sb2SCl6] · CH3CN

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.     

Disulfidoverbrückte Halogenokomplexe von Molybdän(V) Kristallstrukturen von (PPh3Me)2[Cl4Mo(μ-S2)2MoCl4] · 2 CH2Cl2 und (PPh4)2[Br4Mo(μ-S2)2MoBr4] · 3 CH2Br2

Disulfido-Bridged Halo Complexes of Molybdenum (V). Crystal Sructures of (PPh₃Me)₂ [Cl₄Mo (μ-S₂)₂MoCl₄]. 2 CH₂Cl₂ and (PPh₄)₂[Br₄Mo(μ-S₂)₂MoBr₄]. 3CH₂Br₂ . Mo(S₂)Cl₃ is prepared by an improved method; the i.r. spectrum is reported. In dichloro methane solution it reacts with (PPh₃Me)Cl forming the complex (PPh₃Me)₂[Cl₄Mo(μ-S₂)₂MoCl₄] · 2 CH₂Cl₂. The bromo complex (PPh₄)₂[Br₄Mo(μ-S₂)₂MoBr₄] · 3 CH₂Br₂ is obtained by reaction of MoBr₄ with S₇NH and subsequent treatment of the reaction mixture with PPh₄Br in CH₂Br₂ solution. Both complexes are characterized by i.r. spectra and structural analyses by X-ray methods. (PPh₃Me)₂[Cl₄Mo(μ-S₂)₂MoCl₄] · 2 CH₂Cl₂ crystallizes monoclinic in the space group P2₁/c with two formula units per unit cell (5268 observed independent reflexions, R = 4.0%). The lattice dimensions are: a = 1097 pm, b = 1510 pm, c = 1591 pm, β = 104.4°. (PPh₄)₂[Br₄Mo(μ-S₂)₂MoBr₄] · 3 CH₂Br₂ crystallizes triclinic in the space group P&1macr; with two formula units per unit cell and the lattice constants a = 1328 pm, b = 1573 pm, c = 1719 pm, α = 95.8°, β = 96.3°, γ = 74.1°. Both compounds are of ionical structure with PPh₃Me^⊕ and PPh₄^⊕ cations, respectively, and anions [X₄MO(μ-S₂)₂MoX₄]^2? very similar to each other. The molybdenum atoms are bridged by two disulfido ligands and are bonded directly with a bond length of 286 pm. The terminal halogen atoms add up to coordination number nine at the molybdenum.     

Reaktionen von Uranpentabromid Die Kristallstrukturen von PPh4[UBr6], PPh4 [UBr6] · 2CCl4, (PPh4)2[UBr6] · 4CH3CN und (PPh4)2[UO2Br4] · 2CH2Cl2

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 UBr₆^2? and 282.5 pm for UO₂Br₄^2?     

Darstellung und Schwingungsspektren von Dichloro- und Dibromodithiophosphat Die Kristallstrukturen von [PPh3Me] [PS2Cl2] und [PPh4] [PS2Br2]

Preparation and Vibrational Spectra of Dichloro and Dibromodithiophosphate. Crystal Structures of [PPh₃Me][PS₂Cl₂] and [PPh₄][PS₂Br₂] Dichloro and dibromodithiophosphates [Cat⁺][PS₂X₂^?] with a large organic cation can be obtained from P₄S₁₀, CatX and HX in CH₂Cl₂ (Cat⁺ = PPh₄⁺, PPh₃Me⁺; X = Cl, Br). The vibrational spectra (i.r. and Raman) of the [PS₂X₂]^? ions are reported and discussed; force constants were calculated. The crystal structures of [PPh₃Me][PS₂Cl₂] and [PPh₄][PS₂Br₂] were determined and refined with X-ray diffraction data. In both cases, simple anions [PS₂X₂]^? are present. [PPh₃Me][PS₂Cl₂]: orthorhombic, space group P2₁2₁2₁, a = 1089, b = 1334, c = 1476 pm, Z = 4, refinement to a residual index R = 0.046 for 1116 reflexions; the structure is isotopic with [PPh₃Me][VO₂Cl₂]. [PPh₄][PS₂Br₂]: tetragonal space group I4 , a = 1301, c = 721 pm, Z = 2, refinement to R = 0.065 for 357 reflexions; the structure is isotypic with [AsPh₄][FeCl₄] with [PS₂Br₂]^? ions occupying positions of 4 -symmetry with statistical orientation (statistical superposition of Br and S positions).     

Die Bromokomplexe von Molybdän(IV) [MoBr6]2⊖ und [Mo2Br10]2⊖. Die Kristallstruktur von (PPh3Me)2[MoBr6] · 2 CH2Br2

Bromo Complexes of Molybdenum(IV) [MoBr₆]^2? and [Mo₂Br₁₀]^2?. Crystal Structure of (PPh₃Me)₂[MoBr₆] · 2 CH₂Br₂ The bromomolybdates(IV) (PPh₃Me)₂[MoBr₆] · 2 CH₂Br₂ and (PPh₄)₂[Mo₂Br₁₀] are obtained by reactions of molybdenum tetrabromide with PPh₃MeBr and PPh₄Br, respectively. They form black-brown, hydrolysis sensitive crystal powders. The crystal structure of (PPh₃Me)₂[MoBr₆] · 2 CH₂Br₂ was determined by X-ray diffraction (2376 independent observed reflexions, R = 0.082). Crystal data: a = 1024, b = 1131, c = 1179 pm, α = 108.2°, β = 106.8°, γ = 99.0°, space group P1 , Z = 1. The compound consists of PPh₃Me⁺ ions, CH₂Br₂ molecules and nearly octahedral [MoBr₆]^2? ions with MoBr bond lengths between 252.7 and 254.0 pm.     

Synthese und Kristallstrukturen von (PPh4)2[In(S4)(S6)Cl] und (PPh4)2[In(S4)Cl3]

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.     

Thiochlorowolframate von Wolfram(V) und -(VI). Die Kristallstrukturen von PPh4[WSCl4] und (PPh4)2[WS2Cl4] · 2 CH2Cl2

Thiochlorowolframates with Tungsten(V) and (VI). Crystal Structures of PPh₄[WSCl₄] and (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂ Diamagnetic (NEt₄)₂[WSCl₄]₂, having tungsten atoms linked via sulfur atoms, is obtained by the reaction of WCl₅ with NEt₄SH as well as by the reduction of WSCl₄ with NEt₄I in dichloromethane. If the reduction is performed with PPh₄I, PPh₄[WSCl₄] with monomer anions is formed. Reaction of WCl₆ with H₂S in dichloromethane yields brown, insoluble WS₂Cl₂ which has terminal W?S groups and bridging W? S? W groups according to its IR spectrum. WS₂Cl₂ and PPh₄Cl react to afford PPh₄[WS₂Cl₃] · 2 CH₂Cl₂ and (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂. IR spectra are reported. The crystal structures of PPh₄[WSCl₄] and (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂ were determined by X-ray diffraction. PPh₄[WSCl₄]: tetragonal, space group P4/n, Z = 2, a = 1292.3 pm, c = 763.2 pm; R = 0.054 for 898 observed reflexions. The [WSCl₄]^? ion has the structure of a square pyramid with a rather short W?S bond of 206 pm length. (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂: triclinic, space group P1 , a = 1017.7, b = 1114.5, c = 1243.4 pm, α = 70.61, β = 79.73, γ = 80.80°; R = 0.076 for 1804 reflexions. The [WS₂Cl₄]^2? has cis configuration; as it is situated on an inversion center it shows positional disorder.     

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.     

Synthese und Kristallstrukturen von (PPh4)2[As2Se4Cl12] und (PPh4)2[As2Se4Br12]

Synthesis and Crystal Structures of (PPh₄)₂[As₂Se₄Cl₁₂] and (PPh₄)₂[As₂Se₄Br₁₂] The reaction of PPh₄Cl and As₂Se₃ with SOCl₂ or with chlorine in dichloromethane affords (PPh₄)₂[As₂Se₄Cl₁₂] with good yields. From PPh₄Br, As₂Se₃ and bromine the corresponding bromo compound was obtained. According to the X-ray crystal structure determinations both compounds are isotypic, crystallizing in the space group of P1 . In the anions two Se₂X₂ molecules are linked with two X^? ions forming an Se₄X₂ ring in chair conformation. Each X^?-ion is associated with an additional AsX₃ molecule (X = Cl, Br).     

Thiokomplexe des Molybdäns Kristallstruktur eines Mischkristalls (PPh3Me)2[Mo2Br6(NO)4]/(PPh3Me)2[Mo2Br6S2(NO)2]

Thiocomplexes of Molybdenum. Crystal Structure of a Mixed Single Crystal (PPh₃Me)₂[Mo₂Br₆(NO)₄]/(PPh₃Me)₂[Mo₂Br₆S₂(NO)₂] The reactions of (PPh₄)₂MoS₄ with MoBr₄ and MoBr₂(NO)₂ resp. lead to the binuclear complexes (PPh₄)₂[S₂MoS₂MoBr₃(SMe₂)] and (PPh₄)[S₂MoS₂MoBr₂(NO)₂], in which the molybdenum atoms are linked by sulfido bridges. The preparation of (PPh₃Me)₂S₆ and (AsPh₄)₂S₇ from Na₂S₄ and PPh₃MeBr, and AsPh₄Cl, respectively, in ethanol solution is described. Disulfido briges are a feature of (AsPh₄)₂[Mo₂Br₆(S₂)₂(SMe₂)₂], which is obtained from MoBr₄(SMe₂)₂ and (AsPh₄)₂S₇. Mixed single crystals containing 2/3 (PPh₃Me)₂[Mo₂Br₆(NO)₄] and 1/3 (PPh₃Me)₂[Mo₂Br₆S₂(NO)₂] are formed in the reaction of MoBr₂(NO)₂ with (PPh₃Me)₂S₆, as shown by X-ray single crystal structure determination. The compound crystallizes monoclinic in the space group C2/c (Internat. Tab. Nr. 15) with four formula units per unit cell (2351 independent observed reflexions, R_w = 0.037). The cell parameters are a = 1603 pm, b = 1549 pm, c = 1863 pm; β = 92.2°. The complexes consist of PPh₃Me^⊕ cations and the dimeric anions [Mo₂Br₆(NO)₄]^2? and [Mo₂Br₆S₂(NO)₂]^2? which occur in the ratio 2:1. In these the molybdenum atoms are connected via MoBr₂Mo bridges of slightly different lengths (Mo? Br 265 pm and 267 pm) forming a controsymmetric double octahedron. All molybdenum atoms have two terminal bromo ligands with Mo? Br bond lengths of 258 pm and 260 pm; in the [Mo₂Br₆(NO)₄]^2? ion each molybdenum has two covalently bonded nitrosyl groups on cis-position with Mo? N bond lengths of 183 pm. In the [Mo₂Br₆S₂(NO)₂]^2? ion one of the two nitrosyl groups at each metal atom is substituted by a terminal sulfido ligand with a Mo? S bond length of 240 pm. The i.r. spectra are reported.     

Thiohalogeno-Verbindungen von Niob und Tantal: NbSCl3, TaSCl3, [NbSCl5]2−, [TaSCl5]2−, [NbSBr4]− Die Kristallstrukturen von (PPh4)2[NbSCl5] · 2 CH2Cl2 und NEt4[NbCl6]

Thiohalo Compounds of Niobium and Tantalum: NbSCl₃, TaSCl₃, [NbSCl₅]^2?, [TaSCl₅]^2?, [NbSBr₄]^?. Crystal Structures of (PPh₄)₂[NbSCl₅] · 2 CH₂Cl₂ and NEt₄[NbCl₆] NbSCl₃ can be obtained from NbCl₅ by reaction with H₂S or bistrimethylsilyl sulfide in a suspension of CCl₄ or CH₂Cl₂, respectively; in the latter case the product contains a rest of trimethylsilyl groups. This also applies for TaSCl₃, NbSBr₃ and TaSBr₃, which are formed from the metal pentahalides and S(SiMe₃)₂. NEt₄[NbSCl₄] is formed together with NEt₄[NbCl₆] in the reaction of NbCl₅ with NEt₄SH in CH₂Cl₂. PPh₄[NbCl₆] reacts with S(SiMe₃)₂ in dichloromethane yielding (PPh₄)₂[NbSCl₅] · 2 CH₂Cl₂, whereas PPh₄[NbSBr₄] is obtained from PPh₄[NbBr₆] and S(SiMe₃) under the same conditions. (PPh₄)₂[TaSCl₅] · 2 CH₂Cl₂ was obtained from TaSCl₃ and PPh₄Cl in CH₂Cl₂. According to an X-ray crystal structure determination (PPh₄)₂[NbSCl₅] · 2 CH₂Cl₂ crystallizes in the β-(AsPh₄)₂[UCl₆] · 2 CH₂Cl₂ type with positionally disordered, octahedral anions. Crystal data: a = 1 021.7, b = 1120.4, c = 1 243.3 pm, α = 70.77, β = 80.24, γ = 80.54°, space group P1 , Z = 2; 2462 unique observed reflexions, R = 0.036. NEt₄[NbCl₆] crystallizes isotypic to NEt₄[WCl₆], a = 723.5, b = 1 018.0, c = 1 174.6 pm, β = 100.07°, space group P2₁/n, Z = 2; 1 875 reflexions, R = 0.075.     

Die Kristallpackung von (PPh4)2[NiCl4] · 2 MeCN und PPh4[CoCl0,6Br2,4(NCMe)]

The Crystal Packings of (PPh₄)₂[NiCl₄] · 2 MeCN and PPh₄[CoCl_0.6Br_2.4(NCMe)] (PPh₄)₂[NiCl₄] · 2 MeCN was obtained from the reaction of PPh₄Cl and NiCl₂ in acetonitrile in the presence of S₂Cl₂, PPh₄[Cl₂H] being a side product. The product of the reaction of CoS₂ with S₂Br₂ (containing rests of S₂Cl₂) at 400 °C was treated with PPh₄Br in acetonitrile yielding PPh₄Br₃ and PPh₄[CoCl_0.6Br_2.4(NCMe)]. The crystal structures of the title compounds were determined by X‐ray diffraction. (PPh₄)₂[NiCl₄] · 2 MeCN (space group I 4, a = 1839.3 pm, c = 1375.3 pm) has a crystal packing derived from the BiPh₄[ClO₄] structure type with a fourfold increased unit cell and one half of the ClO₄^– positions substituted by pairsof acetonitrile molecules. The crystal structure of PPh₄[CoCl_0.6Br_2.4(NCMe)] (space group I4₁/a, a = 1804.7 pm, c = 3198.8 pm) is related to the AsPh₄[RuNCl₄] type with an eightfold increased unit cell. The [CoCl_0.6Br_2.4(NCMe)]^– ions are disordered in two orientations and some halogen positions are randomly occupied by Cl and Br atoms. Family trees of group–subgroup relations show the symmetry relations.     

Die Chlorooxoarsenate(III) (PPh4)2[As4O2Cl10] · 2 CH3CN und (PPh4)2[As2OCl6] · 3 CH3CN

The Chlorooxoarsenates(III) (PPh₄)₂[As₄O₂Cl₁₀] · 2 CH₃CN and (PPh₄)₂[As₂OCl₆] · 3 CH₃CN (PPh₄)₂[As₂Cl₈] can be prepared from As₂O₃, SOCl₂ and PPh₄Cl in acetonitrile. Its oxidation with chlorine yields PPh₄[AsCl₆]. This was also obtained directly from arsenic, chlorine and PPh₄Cl, (PPh₄)₂[As₄O₂Cl₁₀] · 2 CH₃CN being a side product; the latter was obtained with high yield from AsCl₃, As₂O₃ and PPh₄Cl in acetonitrile. By addition of PPh₄Cl it was converted to (PPh₄)₂[As₂OCl₆] · 3 CH₃CN. According to their X-ray crystal structure analyses, both crystallize in the triclinic space group P 1. The [As₄O₂Cl₁₀]^2– ion can be regarded as a centrosymmetric association product of two Cl₂AsOAsCl₂ molecules and two Cl^– ions, each Cl^– ion being coordinated with all four As atoms. In the [As₂OCl₆]^2– ion the As atoms are linked via the O atom and two Cl atoms.     

AsPh4[W2Cl4(N3S2)3] · CCl4; Synthese und Kristallstruktur

AsPh₄[W₂Cl₄(N₃S₂)₃] · CCl₄; Synthesis and Crystal Structure The title compound was obtained in form of black crystals along with other products by the reaction of H₂S and AsPh₄[WCl₄(N₃S₂)] in dichloromethane and subsequent addition of CCl₄. Its crystal structure was determined by X-ray diffraction (3036 observed reflexions, R = 0.051). Crystal data: triclinic, space group P¯1, Z = 2, a = 1369, b = 1398, c = 1441 pm, α = 64.8, β = 68.02 and γ = 58.1°. The compound consists of AsPh₄^⊕ ions, CCl₄ molecules and [W₂Cl₄(N₃S₂)₃]^? ions. In the latter, one tungsten atom is member of one planar WN₃S₂ ring while the second tungsten atom belongs to two such rings forming a nearly planar S₂N₃WN₃S₂ unit. Two nitrogen atoms of this unit are linked to the other tungsten atom forming a WN₂W ring. Two chloro ligands at each tungsten atom complete the coordination sphere to coordination numbers of six.