CuTi2S4 crystallizes in the monoclinic P2/m space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form TiS6 octahedra that share corners with eight equivalent Ti(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with four equivalent Cu(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. In the second Ti site, Ti(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form TiS6 octahedra that share corners with four equivalent Cu(1)S6 octahedra, corners with eight equivalent Ti(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and faces with two equivalent Cu(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. Cu(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form CuS6 octahedra that share corners with four equivalent Ti(2)S6 octahedra, edges with two equivalent Cu(1)S6 octahedra, edges with four equivalent Ti(1)S6 octahedra, and faces with two equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles are 51°. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Ti(1), two equivalent Ti(2), and two equivalent Cu(1) atoms to form a mixture of distorted edge and corner-sharing STi3Cu2 square pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ti(2), two equivalent Ti(1), and one Cu(1) atom.
CuTi2S4 crystallizes in the monoclinic P2/m space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form TiS6 octahedra that share corners with eight equivalent Ti(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with four equivalent Cu(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. Both Ti(1)-S(1) bond lengths are 2.54 Å. All Ti(1)-S(2) bond lengths are 2.41 Å. In the second Ti site, Ti(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form TiS6 octahedra that share corners with four equivalent Cu(1)S6 octahedra, corners with eight equivalent Ti(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and faces with two equivalent Cu(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. Both Ti(2)-S(2) bond lengths are 2.50 Å. All Ti(2)-S(1) bond lengths are 2.43 Å. Cu(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form CuS6 octahedra that share corners with four equivalent Ti(2)S6 octahedra, edges with two equivalent Cu(1)S6 octahedra, edges with four equivalent Ti(1)S6 octahedra, and faces with two equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles are 51°. Both Cu(1)-S(2) bond lengths are 2.51 Å. All Cu(1)-S(1) bond lengths are 2.46 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Ti(1), two equivalent Ti(2), and two equivalent Cu(1) atoms to form a mixture of distorted edge and corner-sharing STi3Cu2 square pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ti(2), two equivalent Ti(1), and one Cu(1) atom.