Ca3(TiS2)8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent S(4) and four equivalent S(6) atoms to form distorted CaS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, corners with eight equivalent Ti(3)S6 octahedra, and faces with two equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-48°. In the second Ca site, Ca(2) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(5) atoms to form distorted CaS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, corners with four equivalent Ti(2)S6 octahedra, corners with four equivalent Ti(3)S6 octahedra, edges with two equivalent Ca(2)S6 octahedra, and faces with two equivalent Ti(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(2), two equivalent S(5), and two equivalent S(6) atoms to form TiS6 octahedra that share corners with two equivalent Ca(1)S6 octahedra, corners with four equivalent Ca(2)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with four equivalent Ti(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-47°. In the second Ti site, Ti(2) is bonded to one S(3), one S(4), two equivalent S(5), and two equivalent S(6) atoms to form TiS6 octahedra that share corners with four equivalent Ca(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with four equivalent Ti(3)S6 octahedra, and  a faceface with one Ca(1)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. In the third Ti site, Ti(3) is bonded to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom to form TiS6 octahedra that share corners with two equivalent Ca(1)S6 octahedra, corners with two equivalent Ca(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with two equivalent Ti(3)S6 octahedra, and  a faceface with one Ca(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 45-48°. There are six inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ca(2), one Ti(1), and two equivalent Ti(3) atoms to form a mixture of distorted edge and corner-sharing SCa2Ti3 trigonal bipyramids. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(3) atoms. In the third S site, S(3) is bonded to two equivalent Ca(2), one Ti(2), and two equivalent Ti(3) atoms to form a mixture of distorted edge and corner-sharing SCa2Ti3 trigonal bipyramids. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ti(2), and two equivalent Ti(3) atoms. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Ca(2), one Ti(1), one Ti(2), and one Ti(3) atom. In the sixth S site, S(6) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ti(1), one Ti(2), and one Ti(3) atom.
Ca3(TiS2)8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent S(4) and four equivalent S(6) atoms to form distorted CaS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, corners with eight equivalent Ti(3)S6 octahedra, and faces with two equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-48°. Both Ca(1)-S(4) bond lengths are 2.81 Å. All Ca(1)-S(6) bond lengths are 2.81 Å. In the second Ca site, Ca(2) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(5) atoms to form distorted CaS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, corners with four equivalent Ti(2)S6 octahedra, corners with four equivalent Ti(3)S6 octahedra, edges with two equivalent Ca(2)S6 octahedra, and faces with two equivalent Ti(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. Both Ca(2)-S(1) bond lengths are 2.80 Å. Both Ca(2)-S(3) bond lengths are 2.78 Å. Both Ca(2)-S(5) bond lengths are 2.81 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(2), two equivalent S(5), and two equivalent S(6) atoms to form TiS6 octahedra that share corners with two equivalent Ca(1)S6 octahedra, corners with four equivalent Ca(2)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with four equivalent Ti(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-47°. The Ti(1)-S(1) bond length is 2.52 Å. The Ti(1)-S(2) bond length is 2.41 Å. Both Ti(1)-S(5) bond lengths are 2.46 Å. Both Ti(1)-S(6) bond lengths are 2.47 Å. In the second Ti site, Ti(2) is bonded to one S(3), one S(4), two equivalent S(5), and two equivalent S(6) atoms to form TiS6 octahedra that share corners with four equivalent Ca(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with four equivalent Ti(3)S6 octahedra, and  a faceface with one Ca(1)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. The Ti(2)-S(3) bond length is 2.48 Å. The Ti(2)-S(4) bond length is 2.46 Å. Both Ti(2)-S(5) bond lengths are 2.45 Å. Both Ti(2)-S(6) bond lengths are 2.50 Å. In the third Ti site, Ti(3) is bonded to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom to form TiS6 octahedra that share corners with two equivalent Ca(1)S6 octahedra, corners with two equivalent Ca(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with two equivalent Ti(3)S6 octahedra, and  a faceface with one Ca(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 45-48°. The Ti(3)-S(1) bond length is 2.54 Å. The Ti(3)-S(2) bond length is 2.41 Å. The Ti(3)-S(3) bond length is 2.51 Å. The Ti(3)-S(4) bond length is 2.45 Å. The Ti(3)-S(5) bond length is 2.46 Å. The Ti(3)-S(6) bond length is 2.45 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ca(2), one Ti(1), and two equivalent Ti(3) atoms to form a mixture of distorted edge and corner-sharing SCa2Ti3 trigonal bipyramids. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(3) atoms. In the third S site, S(3) is bonded to two equivalent Ca(2), one Ti(2), and two equivalent Ti(3) atoms to form a mixture of distorted edge and corner-sharing SCa2Ti3 trigonal bipyramids. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ti(2), and two equivalent Ti(3) atoms. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Ca(2), one Ti(1), one Ti(2), and one Ti(3) atom. In the sixth S site, S(6) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ti(1), one Ti(2), and one Ti(3) atom.