The crystal structure of SCl3[Re2Cl9] and its relation to the RuBr3 type

SCl3[Re2Cl9] was obtained from the reaction of rhenium and SCl2 at 400 OC. The X-ray crystal structure determination revealed a monoclinic structure, a = 834.1 pm, b = 1053.3 pm, c = 866.1 pm, beta = 91.90 degrees, space grou p P2(1)/m, R-1 = 0.058. The SCl3+ and Re2Cl9- ions have the known structure s; the ReRe bond length in the face-sharing bioctahedron is 272.2 pm. The c rystal packing can be derived from the RuBr3, structure type, which has inf inite columns of face-sharing octahedra; one quarter of the metal atoms are removed and another quarter are replaced by sulfur atoms. The chlorine ato ms form a slightly distorted hexagonal closest-packing. The symmetry relati onships are shown in a family tree of group-subgroup relations.