Die Reaktionen von Trithiazylchlorid mit Molybdän, Molybdäntrioxid und Natriummolybdat. Die Kristallstruktur von PPh4[MoCl4(N3S2)] und ihre Packung / The Reactions of Trithiazyl Chloride with Molybdenum, Molybdenum Trioxide and Sodium Molybdate. The Crystal Structure of PPh4[MoCl4(N3S2)] and its Packing

Abstract

Trithiazylchloride, (NSCl)3, reacts with Mᴏ, MᴏO3 or Na2MᴏO4 at 75 - 80 °C to give high yields of S4N3[MᴏCl4(N3S2)]. By interaction with a solution of PPh4Cl in CH2C12 this product can be converted into PPh4[MoCl4(N3S2)], from which [MᴏCl3(N3S2)]2 can be obtained by reaction with gallium trichloride. The crystal structure of PPh4[MᴏCl4(N3S2)] was determ ined by X-ray diffraction (2436 observed reflexions, R = 0.047). Crystal data: orthorhombic, space group Pbca, Z = 8 , a = 1384.3, b = 2092.4, c = 1898.6 pm. The structure consists of PPh4 + cations and [MᴏCl4(N3S2)]⊕ anions in which the Mo atoms are part of a planar MoN3S2 ring with MoN bond lengths of 183 and 184 pm and nearly equal NS bond lengths (mean value 158 pm). The PPh4 ⊕ ions are arranged in centrosymmetric (PPh4 ⊕)2 pairs in a manner that normally is encountered with doubly charged anions. The structure found for PPh4[MoCl4(N3S2)] differs from the known monoclinic structures of AsPh4[MoCl4(N3S2)] and AsPh4[WCl4(N3S2)]; an analysis of their packing showed that they form layers of AsPh4 ⊕ ions in which three phenyl groups of every AsPh4 ⊕ ion are adjacent to phenyl groups of four other AsPh4 ⊕ ions