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.     

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.     

PPh4[As3S3Cl4] und PPh4[As3S3Br4]

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.     

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.     

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.     

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.     

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).     

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.     

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[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.     

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.     

(PPh4)2[MoN(N3)3Cl]2; Synthese,IR-Spektrum und Kristallstruktur

(PPh₄)₂[MoN(N₃)₃Cl]₂; Synthesis, IR Spectrum, and Crystal Structure The title compound is formed in the reaction of molybdenum (II) benzoate with trimethylsilyl azide and PPh₄Cl in dichloro methane forming dark red single crystals. A PPh₃Me⊕ salt of the ion [MoN(N₃)₃Cl]₂^2? is obtained from (PPh₃Me)₂MoNCl₄] treated with silver azide in CH₂Cl₂ suspension. The solvent CH₂Cl₂ participates in both reactions as oxidizing agent. (PPh₄)₂[MoN(N₃)₃Cl₂ is characterized by a structural analysis based upon X-ray data: space group P1 , Z = 1, a = 1050.7 pm; b = 1185.4 pm; c = 1190.8 pm; α = 98.90°; β = 106.87°; γ = 103.97° (4505 independent, observed reflexions, R = 0.039). The compound consists of PPh₄⊕ cations and centrosymmetric anions [MoN(N₃)₃Cl₂^2? in which the molybdenum atoms are bridged by the N_α atoms of two azide groups; the resulting Mo? N bond lengths are 208 pm and 260 pm. In trans position to the long Mo? N bond the terminal nitrido ligand is situated, the Mo?N distance of 164 pm corresponds to a triple bond. Two terminal azido ligands and the chloro ligand are filling up the coordination sphere of the molybdenum atoms to a coordination number of six. The i.r. spectrum is reported and assigned.     

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.     

Die Kristallstrukturen von [ReCl4(PhCCPh)]2 · 2 CH2Cl2 und von PPh4[ReOCl4]

Crystal Structures of [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂ and PPh₄[ReOCl₄] Single crystals of [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂ were obtained by chilling dilute solutions of the solvate [ReCl₄(PhC?CPh)POCl₃] in CH₂Cl₂. PPh₄[ReOCl₄] was formed by the reaction of the diphenyl acetylene complex [ReCl₅(PhC?CPh)] with PPh₄Cl · H₂O in CH₂Cl₂ solution. [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂: space group P2₁/c, Z = 2, 2244 observed independent reflexions, R = 0.038. Lattice parameters (19°C): a = 987.2 pm; b = 1533.9 pm; c = 1193.8 pm; β = 90.17° The compound forms centrosymmetrical dimeric molecules with ReCl₂Re bridges with Re? Cl distances of 241.2 and 267.6 pm. The longer Re? Cl bond is situated in trans-position to the equatorial, side-on coordinated diphenyl acetylene ligand with mean Re? C distances of 200 pm. PPh₄[ReOCl₄]: space group P4/n, Z = 2, 1487 observed, independent reflexions, R = 0.047. Lattice parameters (19°C): a = b = 1272.0 pm; c = 771.3 pm. The compound crystallizes in the AsPh₄[RuNCl₄] type; it consists of [ReOCl₄]^? anions and PPh₄⁺ cations. The anions are tetragonal with C_4v symmetry and bond lengths Re? O = 165.4 pm and Re? Cl = 232.6 pm; the bond angle OReCl is 106.7°.     

Reaktionen von Zinnchloriden mit Polysulfiden. Die Kristallstrukturen von (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O] und (PPh4)2[SnCl6] · S8 · 2CH3CN

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)₂S_x, 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.     

Addukte des Oxo-tetrachloro-niobat(V)-Ions Bildung,Schwingungsspektren und Kristallstrukturen von PPh4[NbOCl4(OH2)] und (PPh4)2[NbOCl4(O2PCl2)] · 2 CH2Cl2

Adducts of Oxotetrachloro-niobate (V). Formation, Vibrational Spectra, and Crystal Structures of PPh₄[NbOCl₄(OH₂)] and (PPh₄)₂[NbOCl₄(O₂PCl₂)] · 2 CH₂Cl₂ Crystalline (PPh₄)₂[NbOCl₄(O₂PCl₂)] · 2 CH₂Cl₂ was obtained by hydrolysis of PPh₄[NbSCl₄] in the presence of POCl₃ in CH₂Cl₂. Experiments to obtain the same compound from PPh₄Cl, POCl₃, NbCl₅, and H₂O yielded PPh₄[NbOCl₄(OH₂)]. I.R. spectra of both compounds are discussed. The crystal structure determinations with X-ray diffraction data in both cases show quadratic-pyramidal NbOCl₄^? ions to which a molecule of either H₂O or a PO₂Cl₂^? ion is attached in trans-position to the O atom. PPh₄[NbOCl₄(OH₂)]: tetragonal, space group P4/n, a = 1 308, c = 734 pm, Z = 2, packing as in the AsPh₄[RuNCl₄] type; refinement down to R = 0.046 for 681 reflexions. (PPh₄)₂[NbOCl₄(O₂PCl₂)] · 2 CH₂Cl₂: triclinic, space group P1 , a = 1172, b = 1187, c = 2105 pm, α = 88.40, β = 83.20, γ = 71.28°, Z = 2, packing similar as in (AsPh₄)₂[NbOCl₅] · 2 CH₂Cl₂; refinement to R = 0.059 for 2 502 reflexions.     

(PPh4)2[WO2Cl3]2 · 2 CH2Cl2: Synthese,Schwingungsspektrum und Kristallstruktur

(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]₂^2? 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.     

Synthese und Struktur von (PPh4)3[Re2NCl10]

Synthesis and Crystal Structure of (PPh₄)₃[Re₂NCl₁₀] The rhenium(V) nitrido complex (PPh₄)₃[Re₂NCl₁₀] ( 1 ) is obtained from the reaction of (PPh₄)[ReNCl₄] with 1, 3‐dioxan‐(2‐ylmethyl)diphenyl phosphine in CH₂Cl₂/CH₃CN in form of orange red crystals with the composition 1 ·2CH₂Cl₂ crystallizing in the triclinic space group P1¯ with a = 1210.7(2), b = 1232.5(1), c = 2756.3(5) pm, α = 99.68(1)°, β = 100.24(1)°, γ = 98.59(1)° and Z = 2. The crystal structure contains two symmetry independent, centrosymmetrical complex anions [Re₂NCl₁₀]^3‐ with a symmetrical nitrido bridge Re=N=Re and distances Re(1) ‐ N(1) = 181.34(5) and Re(2) ‐ N(2) = 181.51(4) pm.     

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.     

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?