Ti3VS6 crystallizes in the trigonal R-3 space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to six equivalent S(1) atoms to form TiS6 octahedra that share corners with six equivalent V(1)S6 octahedra and edges with six equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. In the second Ti site, Ti(2) is bonded to six equivalent S(1) atoms to form TiS6 octahedra that share corners with three equivalent V(1)S6 octahedra, edges with three equivalent Ti(1)S6 octahedra, edges with three equivalent Ti(2)S6 octahedra, and  a faceface with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles are 48°. V(1) is bonded to six equivalent S(1) atoms to form VS6 octahedra that share corners with six equivalent Ti(1)S6 octahedra, corners with six equivalent Ti(2)S6 octahedra, and faces with two equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. S(1) is bonded in a rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one V(1) atom.
Ti3VS6 crystallizes in the trigonal R-3 space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to six equivalent S(1) atoms to form TiS6 octahedra that share corners with six equivalent V(1)S6 octahedra and edges with six equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. All Ti(1)-S(1) bond lengths are 2.45 Å. In the second Ti site, Ti(2) is bonded to six equivalent S(1) atoms to form TiS6 octahedra that share corners with three equivalent V(1)S6 octahedra, edges with three equivalent Ti(1)S6 octahedra, edges with three equivalent Ti(2)S6 octahedra, and  a faceface with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles are 48°. There are three shorter (2.44 Å) and three longer (2.46 Å) Ti(2)-S(1) bond lengths. V(1) is bonded to six equivalent S(1) atoms to form VS6 octahedra that share corners with six equivalent Ti(1)S6 octahedra, corners with six equivalent Ti(2)S6 octahedra, and faces with two equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. All V(1)-S(1) bond lengths are 2.45 Å. S(1) is bonded in a rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one V(1) atom.