V4ZnS8 crystallizes in the trigonal R-3m space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent S(1) atoms to form VS6 octahedra that share corners with six equivalent Zn(1)S6 octahedra and edges with six equivalent V(2)S6 octahedra. The corner-sharing octahedral tilt angles are 2°. In the second V site, V(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form VS6 octahedra that share edges with two equivalent V(1)S6 octahedra, edges with two equivalent Zn(1)S6 octahedra, and edges with four equivalent V(2)S6 octahedra. Zn(1) is bonded to six equivalent S(1) atoms to form ZnS6 octahedra that share corners with six equivalent V(1)S6 octahedra and edges with six equivalent V(2)S6 octahedra. The corner-sharing octahedral tilt angles are 2°. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one V(1), two equivalent V(2), and one Zn(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to three equivalent V(2) atoms.
V4ZnS8 crystallizes in the trigonal R-3m space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent S(1) atoms to form VS6 octahedra that share corners with six equivalent Zn(1)S6 octahedra and edges with six equivalent V(2)S6 octahedra. The corner-sharing octahedral tilt angles are 2°. All V(1)-S(1) bond lengths are 2.42 Å. In the second V site, V(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form VS6 octahedra that share edges with two equivalent V(1)S6 octahedra, edges with two equivalent Zn(1)S6 octahedra, and edges with four equivalent V(2)S6 octahedra. Both V(2)-S(2) bond lengths are 2.41 Å. All V(2)-S(1) bond lengths are 2.41 Å. Zn(1) is bonded to six equivalent S(1) atoms to form ZnS6 octahedra that share corners with six equivalent V(1)S6 octahedra and edges with six equivalent V(2)S6 octahedra. The corner-sharing octahedral tilt angles are 2°. All Zn(1)-S(1) bond lengths are 2.48 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one V(1), two equivalent V(2), and one Zn(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to three equivalent V(2) atoms.