DOE OSTI2020
CuTi2S4 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are four 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 CuS6 octahedra, corners with eight TiS6 octahedra, edges with two equivalent TiS6 octahedra, edges with two equivalent CuS6 octahedra, and a faceface with one CuS6 octahedra. The corner-sharing octahedra tilt angles range from 45–52°. There are a spread of Ti–S bond distances ranging from 2.40–2.60 Å. In the second Ti+3.50+ site, Ti+3.50+ is bonded to six S2- atoms to form TiS6 octahedra that share corners with two equivalent CuS6 octahedra, corners with eight TiS6 octahedra, edges with two equivalent TiS6 octahedra, edges with two equivalent CuS6 octahedra, and a faceface with one CuS6 octahedra. The corner-sharing octahedra tilt angles range from 46–59°. There are a spread of Ti–S bond distances ranging from 2.41–2.54 Å. In the third Ti+3.50+ site, Ti+3.50+ is bonded to six S2- atoms to form TiS6 octahedra that share corners with two equivalent CuS6 octahedra, corners with eight TiS6 octahedra, edges with two equivalent TiS6 octahedra, edges with two equivalent CuS6 octahedra, and a faceface with one CuS6 octahedra. The corner-sharing octahedra tilt angles range from 46–59°. There are a spread of Ti–S bond distances ranging from 2.41–2.54 Å. In the fourth Ti+3.50+ site, Ti+3.50+ is bonded to six S2- atoms to form TiS6 octahedra that share corners with two equivalent CuS6 octahedra, corners with eight TiS6 octahedra, edges with two equivalent TiS6 octahedra, edges with two equivalent CuS6 octahedra, and a faceface with one CuS6 octahedra. The corner-sharing octahedra tilt angles range from 45–52°. There are a spread of Ti–S bond distances ranging from 2.40–2.60 Å. There are two inequivalent Cu1+ sites. In the first Cu1+ site, Cu1+ is bonded to six S2- atoms to form CuS6 octahedra that share corners with four TiS6 octahedra, corners with four equivalent CuS6 octahedra, edges with four TiS6 octahedra, and faces with two TiS6 octahedra. The corner-sharing octahedra tilt angles range from 46–59°. There are a spread of Cu–S bond distances ranging from 2.33–2.67 Å. In the second Cu1+ site, Cu1+ is bonded to six S2- atoms to form CuS6 octahedra that share corners with four TiS6 octahedra, corners with four equivalent CuS6 octahedra, edges with four TiS6 octahedra, and faces with two TiS6 octahedra. The corner-sharing octahedra tilt angles range from 46–59°. There are a spread of Cu–S bond distances ranging from 2.33–2.67 Å. There are eight 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 5-coordinate geometry to three Ti+3.50+ and two Cu1+ atoms. In the fourth S2- site, S2- is bonded in a 5-coordinate geometry to three Ti+3.50+ and two Cu1+ atoms. In the fifth S2- site, S2- is bonded in a 5-coordinate geometry to three Ti+3.50+ and two Cu1+ atoms. In the sixth S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to three Ti+3.50+ and one Cu1+ atom. In the seventh S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to three Ti+3.50+ and one Cu1+ atom. In the eighth S2- site, S2- is bonded in a 5-coordinate geometry to three Ti+3.50+ and two Cu1+ atoms.