Ca(TiS2)4 crystallizes in the monoclinic C2/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 four equivalent Ti(2)S6 octahedra, corners with eight equivalent Ti(1)S6 octahedra, and faces with two equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-47°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form TiS6 octahedra that share corners with four 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 46-47°. In the second Ti site, Ti(2) is bonded to one S(2), one S(3), and four equivalent S(1) atoms to form TiS6 octahedra that share corners with two equivalent Ca(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with four equivalent Ti(1)S6 octahedra, and  a faceface with one Ca(1)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. There are three inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ti(1), and two equivalent Ti(2) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ti(2), and two equivalent Ti(1) atoms. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent Ti(1) atoms.
Ca(TiS2)4 crystallizes in the monoclinic C2/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 four equivalent Ti(2)S6 octahedra, corners with eight equivalent Ti(1)S6 octahedra, and faces with two equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-47°. Both Ca(1)-S(2) bond lengths are 2.82 Å. All Ca(1)-S(1) bond lengths are 2.82 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form TiS6 octahedra that share corners with four 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 46-47°. Both Ti(1)-S(1) bond lengths are 2.45 Å. Both Ti(1)-S(2) bond lengths are 2.46 Å. Both Ti(1)-S(3) bond lengths are 2.41 Å. In the second Ti site, Ti(2) is bonded to one S(2), one S(3), and four equivalent S(1) atoms to form TiS6 octahedra that share corners with two equivalent Ca(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with four equivalent Ti(1)S6 octahedra, and  a faceface with one Ca(1)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. The Ti(2)-S(2) bond length is 2.48 Å. The Ti(2)-S(3) bond length is 2.40 Å. There are two shorter (2.44 Å) and two longer (2.47 Å) Ti(2)-S(1) bond lengths. There are three inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ti(1), and two equivalent Ti(2) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ti(2), and two equivalent Ti(1) atoms. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent Ti(1) atoms.