Ca(TiS2)2 is Spinel-like structured and crystallizes in the monoclinic C2/c space group. Ca(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form CaS6 octahedra that share corners with six equivalent Ti(1)S4 tetrahedra, edges with two equivalent Ca(1)S6 octahedra, and edges with four equivalent Ti(2)S6 octahedra. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form TiS4 tetrahedra that share corners with six equivalent Ca(1)S6 octahedra and corners with six equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 45-61°. 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 six equivalent Ti(1)S4 tetrahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with four equivalent Ca(1)S6 octahedra. There are two 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 two equivalent Ca(1), one Ti(1), and one Ti(2) atom.
Ca(TiS2)2 is Spinel-like structured and crystallizes in the monoclinic C2/c space group. Ca(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form CaS6 octahedra that share corners with six equivalent Ti(1)S4 tetrahedra, edges with two equivalent Ca(1)S6 octahedra, and edges with four equivalent Ti(2)S6 octahedra. Both Ca(1)-S(1) bond lengths are 2.79 Å. There are two shorter (2.75 Å) and two longer (2.76 Å) Ca(1)-S(2) bond lengths. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form TiS4 tetrahedra that share corners with six equivalent Ca(1)S6 octahedra and corners with six equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 45-61°. Both Ti(1)-S(1) bond lengths are 2.41 Å. Both Ti(1)-S(2) bond lengths are 2.30 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 six equivalent Ti(1)S4 tetrahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with four equivalent Ca(1)S6 octahedra. Both Ti(2)-S(2) bond lengths are 2.52 Å. There are two shorter (2.55 Å) and two longer (2.56 Å) Ti(2)-S(1) bond lengths. There are two 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 two equivalent Ca(1), one Ti(1), and one Ti(2) atom.