The crystal packing in three modifications of PPh4[ReO(S-4)(2)] and PPh4[ReS(S4S)(2)]

Mixed crystals PPh4[ReS(S-4)(2)](0,63)[ReO(S-4)(2)](0,37) were obtained fro m PPh4Cl, ReCl5 and Na2S4 in acetonitrile. Their crystal structure correspo nds to the known structure of this kind of compound (space group P2(1)/n). In a similar reaction with ReBr5 instead of ReCl5, PPh4[ReO(S-4)(2)] was ob tained in small yield. Its triclinic crystal structure was determined by X- ray crystallography (space group P (1) over tilde). It contains cation pair s (PPh4+)(2) such as they have been found in many other instances. In contr ast, the crystal structures of the mixed crystals and of one known modifica tion of PPh4[ReS(S-4)(2)] have PPh4+ columns similar to compounds crystalli zing in the space group P4/n, albeit in a severely distorted manner; their space group P2(1)/n is a subgroup of P4/n with a doubled unit cell. In anot her modification of PPh4[ReS(S-4)(2)] (space group P2(1)/c) the columns are less distorted, but arranged in a different way.