CuTiPS5 – A New Structure Type with a Corrugated Layered Network Structure

Abstract

The reaction of the binary sulfides TiS2 and P4S10 with the elements Cu and S for 10 h at 750 °C and subsequent annealing at 550 °C for 21 d result in the novel compound CuTiPS5, which crystallizes in the triclinic space group P1 with a = 6.8381(12), b = 6.9905(12), c = 14.612(3) Å, α = 90.057(6)°, β = 101.771(7)°, γ = 103.165(7)°, Z = 4, R1 = 1.87 %, wR2 = 4.74 % (all reflections) and represents the first quaternary copper titanium thiophosphate. The crystal structure contains 1∞[Cu2Ti2(PS4)2S2] chains built from TiS6 octahedra and PS4 and CuS4 tetrahedra, which are connected by common edges and linked via common vertices to form layers. The anionic [TiPS5]– partial structure has been found previously, whereas the distinct 2D extension of the network is observed for the first time in compounds with such a MTiPS5 composition. The structure resembles sections of the TiS2 and Cu3PS4 structures, which were found in the reaction as by-products.