PREPARATION AND CRYSTAL-STRUCTURE OF [SCL 3][MOOCL4]

The reaction of sulfur with MoOCl4 in the presence of a large excess o f ICl3 in a sealed evacuated ampoule at 100 degrees C yields [SCl3][Mo OCl4] in the form of yellow-brown, moisture sensitive crystals. The cr ystal structure determination (monoclinic space group P2(1)/n; lattice constants a=971,1(1) pm, b=926,9(1) pm, c=1220,6(1) pm, beta=112,68(1 )degrees, Z=4) shows that the title compound consists of square pyrami dal [MoOCl4](-) anions and trigonal pyramidal [SCl3](+) cations. Two [ MoOCl4](-) anions are linked by asymmetric chlorine bridges and form c entrosymmetric dimers [Mo2O2Cl8](2-) with the oxygen atoms located in the trans positions of the chlorine bridges. Two trigonal pyramidal [S Cl3](+) cations are connected by secondary sulfur chlorine interaction s with the [Mo2O2Cl8] anion to form centrosymmetric dimers ([SCl3][MoO Cl4])(2). The coordination sphere for the sulfur atom is a strongly di storted octahedron with three S-Cl bonds of 199 pm and three weak S-Cl contacts of 304 pm in average length.