Abstract: | LiTiCl3 is obtained as one example within an ample solid solution, Li24–2nTinCl24 (?4?n?10), by synpropotionation of TiCl3 and Ti in the presence of LiCl (2:1:3 molar ratio) in sealed tantalum tubes at 750°C. It crystallizes with the inverse spinel-type structure according to (Li0.67)4](Li0.67Ti1.33)4]Cl4 with, at 25°C, a = 1048.62(4) pm, space group Fd3m. Thermal expansion is linear with α = 4.85 × 10?5K?1 up to about 300°C and thereafter, when the migration of Li+ from tetrahedral to octahedral interstices becomes increasingly important, it exhibits a relative decrease resulting, finally, in the phase transition to a NaCl-type structure that is observed for the first time at about 575°C. |