CuTiPS 5 – A New Structure Type with a Corrugated Layered Network Structure

The reaction of the binary sulfides TiS 2 and P 4 S 10 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 CuTiPS 5 , which crystallizes in the triclinic space group P 1 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, R 1 = 1.87 %, wR 2 = 4.74 % (all reflections) and represents the first quaternary copper titanium thiophosphate. The crystal structure contains 1 ∞ [Cu 2 Ti 2 (PS 4 ) 2 S 2 ] chains built from TiS 6 octahedra and PS 4 and CuS 4 tetrahedra, which are connected by common edges and linked via common vertices to form layers. The anionic [TiPS 5 ] – 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 M TiPS 5 composition. The structure resembles sections of the TiS 2 and Cu 3 PS 4 structures, which were found in the reaction as by‐products.