Ti3VS4 is Caswellsilverite-like structured and crystallizes in the monoclinic P2/m space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form TiS6 octahedra that share corners with four equivalent Ti(3)S6 octahedra, corners with eight equivalent Ti(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with four equivalent V(1)S6 octahedra, and faces with two equivalent Ti(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-45°. In the second Ti site, Ti(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form TiS6 octahedra that share corners with four equivalent V(1)S6 octahedra, corners with eight equivalent Ti(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with four equivalent Ti(3)S6 octahedra, and faces with two equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-45°. In the third Ti site, Ti(3) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form TiS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, corners with eight equivalent V(1)S6 octahedra, edges with two equivalent Ti(3)S6 octahedra, edges with four equivalent Ti(2)S6 octahedra, and faces with two equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-45°. V(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form VS6 octahedra that share corners with four equivalent Ti(2)S6 octahedra, corners with eight equivalent Ti(3)S6 octahedra, edges with two equivalent V(1)S6 octahedra, edges with four equivalent Ti(1)S6 octahedra, and faces with two equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-45°. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Ti(1), one Ti(3), two equivalent Ti(2), and two equivalent V(1) atoms to form distorted STi4V2 pentagonal pyramids that share corners with six equivalent S(1)Ti4V2 pentagonal pyramids, edges with four equivalent S(1)Ti4V2 pentagonal pyramids, and edges with eight equivalent S(2)Ti5V pentagonal pyramids. In the second S site, S(2) is bonded to one Ti(2), two equivalent Ti(1), two equivalent Ti(3), and one V(1) atom to form distorted STi5V pentagonal pyramids that share corners with six equivalent S(2)Ti5V pentagonal pyramids, edges with four equivalent S(2)Ti5V pentagonal pyramids, and edges with eight equivalent S(1)Ti4V2 pentagonal pyramids.
Ti3VS4 is Caswellsilverite-like structured and crystallizes in the monoclinic P2/m space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form TiS6 octahedra that share corners with four equivalent Ti(3)S6 octahedra, corners with eight equivalent Ti(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with four equivalent V(1)S6 octahedra, and faces with two equivalent Ti(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-45°. Both Ti(1)-S(1) bond lengths are 2.46 Å. All Ti(1)-S(2) bond lengths are 2.46 Å. In the second Ti site, Ti(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form TiS6 octahedra that share corners with four equivalent V(1)S6 octahedra, corners with eight equivalent Ti(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with four equivalent Ti(3)S6 octahedra, and faces with two equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-45°. Both Ti(2)-S(2) bond lengths are 2.45 Å. All Ti(2)-S(1) bond lengths are 2.47 Å. In the third Ti site, Ti(3) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form TiS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, corners with eight equivalent V(1)S6 octahedra, edges with two equivalent Ti(3)S6 octahedra, edges with four equivalent Ti(2)S6 octahedra, and faces with two equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-45°. Both Ti(3)-S(1) bond lengths are 2.49 Å. All Ti(3)-S(2) bond lengths are 2.48 Å. V(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form VS6 octahedra that share corners with four equivalent Ti(2)S6 octahedra, corners with eight equivalent Ti(3)S6 octahedra, edges with two equivalent V(1)S6 octahedra, edges with four equivalent Ti(1)S6 octahedra, and faces with two equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-45°. Both V(1)-S(2) bond lengths are 2.43 Å. All V(1)-S(1) bond lengths are 2.44 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Ti(1), one Ti(3), two equivalent Ti(2), and two equivalent V(1) atoms to form distorted STi4V2 pentagonal pyramids that share corners with six equivalent S(1)Ti4V2 pentagonal pyramids, edges with four equivalent S(1)Ti4V2 pentagonal pyramids, and edges with eight equivalent S(2)Ti5V pentagonal pyramids. In the second S site, S(2) is bonded to one Ti(2), two equivalent Ti(1), two equivalent Ti(3), and one V(1) atom to form distorted STi5V pentagonal pyramids that share corners with six equivalent S(2)Ti5V pentagonal pyramids, edges with four equivalent S(2)Ti5V pentagonal pyramids, and edges with eight equivalent S(1)Ti4V2 pentagonal pyramids.