Ti5S8 crystallizes in the monoclinic C2/m space group. There are three 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 a mixture of corner and edge-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles are 49°. In the second Ti site, Ti(2) is bonded to one S(1), one S(3), and four equivalent S(2) atoms to form a mixture of face, corner, and edge-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles are 50°. In the third Ti site, Ti(3) is bonded to two equivalent S(3) and four equivalent S(2) atoms to form a mixture of face and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent Ti(1) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(3), 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), one Ti(3), and two equivalent Ti(1) atoms.
Ti5S8 crystallizes in the monoclinic C2/m space group. There are three 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 a mixture of corner and edge-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles are 49°. Both Ti(1)-S(1) bond lengths are 2.38 Å. Both Ti(1)-S(2) bond lengths are 2.46 Å. Both Ti(1)-S(3) bond lengths are 2.49 Å. In the second Ti site, Ti(2) is bonded to one S(1), one S(3), and four equivalent S(2) atoms to form a mixture of face, corner, and edge-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles are 50°. The Ti(2)-S(1) bond length is 2.40 Å. The Ti(2)-S(3) bond length is 2.47 Å. There are two shorter (2.44 Å) and two longer (2.49 Å) Ti(2)-S(2) bond lengths. In the third Ti site, Ti(3) is bonded to two equivalent S(3) and four equivalent S(2) atoms to form a mixture of face and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. Both Ti(3)-S(3) bond lengths are 2.46 Å. All Ti(3)-S(2) bond lengths are 2.45 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent Ti(1) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(3), 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), one Ti(3), and two equivalent Ti(1) atoms.