LiTiCl 3 : Synthesis and thermal behaviour

LiTiCl 3 is obtained as one example within an ample solid solution, Li 24–2n Ti n Cl 24 (≃4⩽n⩽10), by synpropotionation of TiCl 3 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 (Li 0.67 ) [4] (Li 0.67 Ti 1.33 ) [4] Cl 4 with, at 25°C, a = 1048.62(4) pm, space group Fd3m. Thermal expansion is linear with α = 4.85 × 10 −5 K −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.