Ti3FeS6 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 Fe(1)S6 octahedra and edges with six equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles are 48°. 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 Fe(1)S6 octahedra, edges with three equivalent Ti(1)S6 octahedra, edges with three equivalent Ti(2)S6 octahedra, and  a faceface with one Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles are 48°. Fe(1) is bonded to six equivalent S(1) atoms to form FeS6 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 are 48°. S(1) is bonded in a rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one Fe(1) atom.
Ti3FeS6 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 Fe(1)S6 octahedra and edges with six equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles are 48°. All Ti(1)-S(1) bond lengths are 2.44 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 Fe(1)S6 octahedra, edges with three equivalent Ti(1)S6 octahedra, edges with three equivalent Ti(2)S6 octahedra, and  a faceface with one Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles are 48°. All Ti(2)-S(1) bond lengths are 2.45 Å. Fe(1) is bonded to six equivalent S(1) atoms to form FeS6 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 are 48°. All Fe(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 Fe(1) atom.