Tris(ethyldimethylphenylammonium) nonahalogenodibismuthates(III)

The halogenobismuthates Q(3)Bi(2)X(9) (Q = EtMe2PhN; X = Cl, Br, I) were pr epared by reaction of BiX3 with EtMe2PhNX in ethanol. Single crystal struct ure determinations yielded: [EtMe2PhN](3)[Bi2Cl9], S. G. P2(1)2(1)2(1), NI. 19, alpha = 952.5(3), b = 1183.1(4), c = 3726.4(9 pm, Z = 2; [EtMe2PhN](3) [Bi2Br9] S. G. P2(1)/c, No. 14, a = 1839.4(4), b = 1329.5(3), c = 1817.3(6) pm, beta = 92.68(3)degrees, Z = 3, [EtMe2PhN](3)[Bi2I9], S. G. P2(1)/c, No. 14, a = 1915.3(2), b = 1379.0(3), c = 1890.9(5) pm, beta = 92.48(1)degrees , Z = 4 The thermal behaviour was investigated with the aid of DSC measurem ents and temperature dependent X-ray powder diffraction. All compounds unde rgo a transition into a high temperature modification which could be obtain ed in case of [EtMe2PhN](3)[Bi2Br9-chiIx] in form of single crystals: S. G. P2(1)/c, Nr. 14, (2 = 1002.7(5), b = 1278.7 (8), c = 3584.3(5) pm, beta = 90.12(2)degrees, Z = 4. Surprisingly in this compound the iodine atoms are not statistically distributed over all possible bromine positions, but occu py only one position. Lattice parameters of the other high temperature modi fications and enthalpies of transition of the compounds are given. In addit ion a second iodobismuthate was isolated: [EtMe2PhN](4)[Bi6I22], S. G. pi, Nr. 2, with lattice parameters of a = 1343.4(3), b = 1554.3(3), c = 2262.5( 6) pm, alpha = 100.89(3)degrees, beta = 96.63(1)degrees, gamma = 98.94(2)de grees and Z = 2.