The crystal packings of (PPh4)(2)[NiCl4]center dot 2 MeCN and PPh4[CoCl0.6Br2.4(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 degreesC was treated with PPh4Br in acetonitrile yielding PPh4Br3 an d PPh4[CoCl0.6Br2.4(NCMe)]. The crystal structures of the title compounds w ere determined by X-ray diffraction. (PPh4)(2)[NiCl4]. 2MeCN (space group l (4) over bar, 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 pairs of acetonitrile molecules . The crystal structure of PPh4[CoCl0.6Br2.4(NCMe)] (space group I4(1)/a, a =1804.7 pm, c=3198.8 pm) is related to the AsPh4[RuNCl4] type with an eight fold increased unit cell. The [CoCl0.6Br2.4(NCMe)] ions are disordered in t wo orientations and some halogen positions are randomly occupied by C1 and Br atoms. Family trees of group-subgroup relations show the symmetry relati ons.