Ca(TiS2)2 crystallizes in the monoclinic P2/m space group. Ca(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form distorted CaS6 octahedra that share corners with six equivalent Ti(1)S6 octahedra, edges with two equivalent Ca(1)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with four equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form TiS6 octahedra that share corners with six equivalent Ca(1)S6 octahedra, edges with two equivalent Ca(1)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with four equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. In the second Ti site, Ti(2) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form TiS6 octahedra that share edges with two equivalent Ti(2)S6 octahedra, edges with four equivalent Ca(1)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ca(1), one Ti(2), and two equivalent Ti(1) atoms to form a mixture of edge and corner-sharing SCa2Ti3 square pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ti(1), and two equivalent Ti(2) atoms.
Ca(TiS2)2 crystallizes in the monoclinic P2/m space group. Ca(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form distorted CaS6 octahedra that share corners with six equivalent Ti(1)S6 octahedra, edges with two equivalent Ca(1)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with four equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. Both Ca(1)-S(2) bond lengths are 2.78 Å. All Ca(1)-S(1) bond lengths are 2.76 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form TiS6 octahedra that share corners with six equivalent Ca(1)S6 octahedra, edges with two equivalent Ca(1)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with four equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. Both Ti(1)-S(2) bond lengths are 2.44 Å. All Ti(1)-S(1) bond lengths are 2.49 Å. In the second Ti site, Ti(2) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form TiS6 octahedra that share edges with two equivalent Ti(2)S6 octahedra, edges with four equivalent Ca(1)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. Both Ti(2)-S(1) bond lengths are 2.49 Å. All Ti(2)-S(2) bond lengths are 2.48 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ca(1), one Ti(2), and two equivalent Ti(1) atoms to form a mixture of edge and corner-sharing SCa2Ti3 square pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ti(1), and two equivalent Ti(2) atoms.