TiS2 crystallizes in the trigonal R3m space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(3) and three equivalent S(4) atoms to form corner-sharing TiS4 tetrahedra. The corner-sharing octahedral tilt angles are 60°. In the second Ti site, Ti(2) is bonded to one S(1), one S(3), two equivalent S(2), and two equivalent S(4) atoms to form TiS6 octahedra that share corners with three equivalent Ti(1)S4 tetrahedra and edges with four equivalent Ti(2)S6 octahedra. There are four inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to three equivalent Ti(2) atoms. In the second S site, S(2) is bonded in an L-shaped geometry to two equivalent Ti(2) atoms. In the third S site, S(3) is bonded in a distorted tetrahedral geometry to one Ti(1) and three equivalent Ti(2) atoms. In the fourth S site, S(4) is bonded in a distorted trigonal planar geometry to one Ti(1) and two equivalent Ti(2) atoms.
TiS2 crystallizes in the trigonal R3m space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(3) and three equivalent S(4) atoms to form corner-sharing TiS4 tetrahedra. The corner-sharing octahedral tilt angles are 60°. The Ti(1)-S(3) bond length is 2.45 Å. All Ti(1)-S(4) bond lengths are 2.26 Å. In the second Ti site, Ti(2) is bonded to one S(1), one S(3), two equivalent S(2), and two equivalent S(4) atoms to form TiS6 octahedra that share corners with three equivalent Ti(1)S4 tetrahedra and edges with four equivalent Ti(2)S6 octahedra. The Ti(2)-S(1) bond length is 2.40 Å. The Ti(2)-S(3) bond length is 2.55 Å. Both Ti(2)-S(2) bond lengths are 2.28 Å. Both Ti(2)-S(4) bond lengths are 2.61 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to three equivalent Ti(2) atoms. In the second S site, S(2) is bonded in an L-shaped geometry to two equivalent Ti(2) atoms. In the third S site, S(3) is bonded in a distorted tetrahedral geometry to one Ti(1) and three equivalent Ti(2) atoms. In the fourth S site, S(4) is bonded in a distorted trigonal planar geometry to one Ti(1) and two equivalent Ti(2) atoms.