The orientation of the Re2Cl82- ions in (PPh4)(2)[Re2Cl8]center dot 2L (L = acetonitrile, dichloromethane)

(PPh4)(2)[Re2Cl8]. 2MeCN was obtained in small yields from PPh4Cl and ReCl5 in the presence of Na2S4 or K2S5 in acetontrile. Its crystal structure was determined by X-ray diffraction, The crystals are nearly isotypic with tho se of (PPh4)(2)[Re2Cl8]. 2CH(2)Cl(2). The pph(4)(+) ions, the solvent molec ules and the chlorine atoms occupy nearly identical positions in both tricl inic structures. Nevertheless, 98% of the Re drop Re groups are differently oriented within the slightly elongated Cls cubes surrounding them. The spa ce requirement of the elongated cubes seems to be more important for the or ientation than electrostatic forces. The PPh4+ ions form (PPh4+)(2) pairs a round inversion centers.