Lithium vanadium chlorides-phase transition, crystal structure of the mixed valence compound Li1.3V1.2Cl4

Single crystals of the mixed valence compound Li1.3V1.2Cl4 were grown by vapor-phase transport of Li2VCl4 using VCl3 as transporting agent. They crystallize in the cubic space group F 43m (Z = 8) with Li(1) and vacancies D at the tetrahedral 4a and 4c sites, and Li(2) and V (occupation factors: 0.397(4) and 0.603(4)) at the octahedral 16e site, respectively, as revealed by X-ray single-crystal structure determination (a = 1035.7(1) pm, 162 unique reflections, Rw= 1.6%). Phase transition of likewise MgCr2O4-type Li2VCl4 to a Zr3S4-type high-temperature polymorph above 600 K was revealed by high-temperature X-ray experiments and DSC measurements.