Oxide Addition to a Reactive Polysulfide Flux: Synthesis of K4Ba[Ti6OS20] Containing Isolated [Ti6OS8(S2)6]6− Clusters

Abstract

Two crystal modifications of the title compound are synthesized by the reactive flux method from K 2 S, BaS, Ti, TiO 2 , and S (hexagonal modification: 823 K, 3 d, 80% yield, orthorhombic modification: 873 K, 2 d, 70% yield). As revealed by single crystal XRD, the hexagonal modification crystallizes in the space group P6 3 22 with Z = 2 and the orthorhombic modification in the space group Fddd with Z = 8. Both modifications consist of well-separated [Ti 6 OS 8 (S 2 ) 6 ] 6− anionic clusters and K + and Ba