TiMoS3 crystallizes in the monoclinic P2_1/m space group. Ti(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form TiS6 octahedra that share corners with six equivalent Mo(1)S6 octahedra, edges with six equivalent Ti(1)S6 octahedra, and  a faceface with one Mo(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-51°. Mo(1) is bonded to one S(2), two equivalent S(1), and three equivalent S(3) atoms to form distorted MoS6 octahedra that share corners with six equivalent Ti(1)S6 octahedra, edges with four equivalent Mo(1)S6 octahedra, and  a faceface with one Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-51°. There are three inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Ti(1) and two equivalent Mo(1) atoms to form distorted edge-sharing STi3Mo2 trigonal bipyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to three equivalent Ti(1) and one Mo(1) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to three equivalent Mo(1) atoms.
TiMoS3 crystallizes in the monoclinic P2_1/m space group. Ti(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form TiS6 octahedra that share corners with six equivalent Mo(1)S6 octahedra, edges with six equivalent Ti(1)S6 octahedra, and  a faceface with one Mo(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-51°. There are two shorter (2.46 Å) and one longer (2.54 Å) Ti(1)-S(1) bond length. There are two shorter (2.42 Å) and one longer (2.45 Å) Ti(1)-S(2) bond length. Mo(1) is bonded to one S(2), two equivalent S(1), and three equivalent S(3) atoms to form distorted MoS6 octahedra that share corners with six equivalent Ti(1)S6 octahedra, edges with four equivalent Mo(1)S6 octahedra, and  a faceface with one Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-51°. The Mo(1)-S(2) bond length is 2.54 Å. Both Mo(1)-S(1) bond lengths are 2.61 Å. There is one shorter (2.36 Å) and two longer (2.39 Å) Mo(1)-S(3) bond lengths. There are three inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Ti(1) and two equivalent Mo(1) atoms to form distorted edge-sharing STi3Mo2 trigonal bipyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to three equivalent Ti(1) and one Mo(1) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to three equivalent Mo(1) atoms.