Materials Data on Ti2CuS4 by Materials Project

Abstract

CuTi2S4 is Spinel-like structured and crystallizes in the trigonal R-3m space group. The structure is three-dimensional. there are three inequivalent Ti+3.50+ sites. In the first Ti+3.50+ site, Ti+3.50+ is bonded to six S2- atoms to form TiS6 octahedra that share corners with two equivalent TiS6 octahedra, corners with four CuS4 tetrahedra, edges with five TiS6 octahedra, and an edgeedge with one CuS4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. There are two shorter (2.45 Å) and four longer (2.47 Å) Ti–S bond lengths. In the second Ti+3.50+ site, Ti+3.50+ is bonded to six equivalent S2- atoms to form TiS6 octahedra that share corners with twelve equivalent TiS6 octahedra and corners with six equivalent CuS4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. All Ti–S bond lengths are 2.47 Å. In the third Ti+3.50+ site, Ti+3.50+ is bonded to six equivalent S2- atoms to form TiS6 octahedra that share corners with six equivalent CuS4 tetrahedra and edges with six equivalent TiS6 octahedra. All Ti–S bond lengths are 2.44 Å. There are two inequivalent Cu1+ sites. In the first Cu1+ site, Cu1+ is bonded to four S2- atoms to form CuS4 tetrahedra that share corners with six TiS6 octahedra and edges with three equivalent TiS6 octahedra. The corner-sharing octahedra tilt angles range from 56–59°. There are one shorter (2.24 Å) and three longer (2.27 Å) Cu–S bond lengths. In the second Cu1+ site, Cu1+ is bonded to four S2- atoms to form CuS4 tetrahedra that share corners with twelve TiS6 octahedra. The corner-sharing octahedra tilt angles range from 56–57°. All Cu–S bond lengths are 2.26 Å. There are four inequivalent S2- sites. In the first S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to three Ti+3.50+ and one Cu1+ atom. In the second S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to three Ti+3.50+ and one Cu1+ atom. In the third S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to three equivalent Ti+3.50+ and one Cu1+ atom. In the fourth S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to three equivalent Ti+3.50+ and one Cu1+ atom.