Ti3CoS6 crystallizes in the hexagonal P6_322 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 distorted TiS6 pentagonal pyramids that share corners with six equivalent Co(1)S6 octahedra. The corner-sharing octahedral tilt angles are 46°. In the second Ti site, Ti(2) is bonded in a 6-coordinate geometry to six equivalent S(1) atoms. Co(1) is bonded to six equivalent S(1) atoms to form CoS6 octahedra that share corners with six equivalent Ti(1)S6 pentagonal pyramids. S(1) is bonded in a rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one Co(1) atom.
Ti3CoS6 crystallizes in the hexagonal P6_322 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 distorted TiS6 pentagonal pyramids that share corners with six equivalent Co(1)S6 octahedra. The corner-sharing octahedral tilt angles are 46°. All Ti(1)-S(1) bond lengths are 2.45 Å. In the second Ti site, Ti(2) is bonded in a 6-coordinate geometry to six equivalent S(1) atoms. There are three shorter (2.43 Å) and three longer (2.44 Å) Ti(2)-S(1) bond lengths. Co(1) is bonded to six equivalent S(1) atoms to form CoS6 octahedra that share corners with six equivalent Ti(1)S6 pentagonal pyramids. All Co(1)-S(1) bond lengths are 2.30 Å. S(1) is bonded in a rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one Co(1) atom.