Synthesis and thermal behaviour of compounds in the system [Ph4P]Cl/BiCl3 and the crystal structures of [Ph4P](3)[Bi2Cl9]center dot 2 CH2Cl2 and [Ph4P](2)[Bi2Cl8]center dot 2 CH3COCH3

Six polynuclear chlorobismuthates are formed in the reaction between BiCl3 and Ph4PCl by variation of the molar ratio of the educts, the solvents and the crystallisation methods: [Ph4P](3)[Bi2Cl9].2 CH2Cl2, [Ph4P](3)[Bi2Cl9]. CH3COCH3, [Ph4Ph](2)[Bi2Cl9] . 2 CH3COCH3, [Ph4P](4)[Bi4Cl16] . 3 CH3CN, [ Ph4P](4)[Bi6Cl22]. and [Ph4P](4)[Bi8Cl28]. We report the crystal structure of [Ph4P]3[Bi2Cl9] . 2 CH2Cl2 which crystallises with triclinic symmetry in the S. G. P (1) over bar No. 2, with the lattice parameters a = 13.080(3) Angstrom, b 14.369(3) Angstrom. c = 21.397(4) Angstrom, alpha = 96.83(l)deg rees, beta = 95.96(l)degrees, gamma = 95.94(2)degrees, V = 3943.9(l) Angstr om (3), Z = 2. The anion is formed from two face-sharing BiCl6-octahedra. [ Ph4P](2)[Bi2Cl8] . 2 CH3COCH3 crystallises with monoclinic symmetry in the S; G. P2(1)/n, No. 14, with the lattice parameters a = 14.045(5) Angstrom, b = 12.921(4) Angstrom, c = 17.098(3) Angstrom. beta = 111. 10(2)degrees, V = 2894.8(2) Angstrom (3). Z = 2. The anion is a bi-octahedron of two squar e-pyramids, joined by a common edge. The octahedral coordination is achieve d with two acetone ligands. [Ph4P](4)[Bi4Cl16] . 3CH(3)CN crystallises in t he triclinic S. G., P (1) over bar, No. 2, with the lattice parameters a = 14.245(9) Angstrom, b = 17.318(6)Angstrom, c = 24.475(8) Angstrom. alpha = 104.66(3)degrees, beta = 95.93(3)degrees, gamma = 106.90(4)degrees. V = 548 6(4) Angstrom (3), Z = 2. Two Bi2Cl8 dimers in syn-position form the cubic anion. Lattice parameters of [Ph4P](3)[Bi2Cl9] . CH3COCH3 are also given. T he solvated compounds are desolvated at approximately 100 degreesC. [Ph4P]( 3)[Bi2Cl9] . 2CH(2)Cl(2) and [Ph4P](3)[Bi2Cl9] . CH3COCH3 show the same seq uence of phase transitions after desolvation. All compounds melt into a liq uid in which some order is observed and transform on cooling into the glass y state.