A synthesis route for carbon-centered triprismo-hexatungsten cluster compounds and the crystal structure of Cs[W6CCl18]•CH3OH

Li-x[W6CCl18] was synthesized by the reaction of WCl4 with Li2CN2, and used as source material for the synthesis of a new carbon-centered triprismo-hexatungsten cluster compound. Black crystals of Cs[W6CCl18].CH3OH were obtained by cation-exchange reaction of Li-x[W6CCl18] with CsCl in methanol. The air-stable compound crystallizes orthorhombic with unit-cell parameters a = 9.6957(5) angstrom, b = 14.046(1) angstrom, and c = 20.238(1) angstrom in the space group P2(1)2(1)2(1) (No. 19). The crystal structure of Cs[W6CCl18].CH3OH contains isolated [W6CCl18](-) ions. If these ions are considered as spheres, their arrangement in the structure follows the principle of hexagonal closest packing, with cesium ions and methanol molecules filling voids in the hexagonal cluster layers.