(PPh4)2[V2Cl9][VCl5] · CH2Cl2 Synthese,IR-Spektrum und Kristallstruktur

(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 D_3h symmetry. Half of the cations is arranged to (PPh₄⁺)₂ pairs about inversion centers.