Ti4CoS8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(2), and four equivalent S(3) atoms to form TiS6 octahedra that share corners with two equivalent Co(1)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with four equivalent Ti(2)S6 octahedra, and  a faceface with one Co(1)S6 octahedra. The corner-sharing octahedral tilt angles are 49°. In the second Ti site, Ti(2) 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 Co(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles are 48°. Co(1) is bonded to two equivalent S(1) and four equivalent S(3) atoms to form CoS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, corners with eight equivalent Ti(2)S6 octahedra, and faces with two equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-49°. There are three inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one Co(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(2) atoms. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Ti(2), two equivalent Ti(1), and one Co(1) atom.
Ti4CoS8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(2), and four equivalent S(3) atoms to form TiS6 octahedra that share corners with two equivalent Co(1)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with four equivalent Ti(2)S6 octahedra, and  a faceface with one Co(1)S6 octahedra. The corner-sharing octahedral tilt angles are 49°. The Ti(1)-S(1) bond length is 2.44 Å. The Ti(1)-S(2) bond length is 2.40 Å. All Ti(1)-S(3) bond lengths are 2.44 Å. In the second Ti site, Ti(2) 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 Co(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles are 48°. Both Ti(2)-S(1) bond lengths are 2.45 Å. Both Ti(2)-S(2) bond lengths are 2.40 Å. Both Ti(2)-S(3) bond lengths are 2.45 Å. Co(1) is bonded to two equivalent S(1) and four equivalent S(3) atoms to form CoS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, corners with eight equivalent Ti(2)S6 octahedra, and faces with two equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-49°. Both Co(1)-S(1) bond lengths are 2.42 Å. All Co(1)-S(3) bond lengths are 2.40 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one Co(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(2) atoms. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Ti(2), two equivalent Ti(1), and one Co(1) atom.