SYNTHESES AND CRYSTAL-STRUCTURES OF THE THIOCHLOROANTIMONATES(III) PPH4[SB2SCL5] AND (PPH4)2[SB2SCL6] BULLET CH3CN

(PPh4)2Sb3Cl11, obtained from Sb2S3, PPh4Cl and HCl, reacts with Na2S4 in acetonitrile forming PPh4[Sb2SCl5]. From this and Na2S4 or from (PPh4)2[Sb2Cl8] and Na2S4 or K2S5 in acetonitrile (PPh4)2[Sb2SCl6] . CH3CN is obtained. Data obtained from the X-ray crystal structure determinations are: PPh4[Sb2SCl5], monoclinic, space group P2(1)/c, a = 1002.9(3), b = 1705.6(5), c = 1653.7(5) pm, beta = 99.12(2)-degrees, Z = 4, R = 0.068 for 1 283 reflexions; (PPh4)2[Sb2SCl6] . CH3CN, triclinic, space group P1BAR, a = 1287.8(7), b = 1343.6(9), c = 1696.5(9) pm, alpha = 69.82(5), beta = 85.08(4), gamma = 71.54(6)-degrees, Z = 2, R = 0.059 for 6409 reflexions. In every anion two Sb atoms are linked via one sulfur and one ore two chloro atoms, respectively. Paris of [SbSCl5]- ions are associated via Sb...S and Sb...Cl contacts forming dimer units. In both compounds every Sb atom has a distorted octahedral coordination when the lone electron pair is included in the counting.