V3S4 crystallizes in the monoclinic C2/m space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 7-coordinate geometry to three equivalent S(1) and four equivalent S(2) atoms. In the second V site, V(2) is bonded in a 4-coordinate geometry to four equivalent S(1) and four equivalent S(2) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent V(2) and three equivalent V(1) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent V(2) and four equivalent V(1) atoms.
V3S4 crystallizes in the monoclinic C2/m space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 7-coordinate geometry to three equivalent S(1) and four equivalent S(2) atoms. There are two shorter (2.44 Å) and one longer (2.55 Å) V(1)-S(1) bond length. There are two shorter (2.42 Å) and two longer (2.50 Å) V(1)-S(2) bond lengths. In the second V site, V(2) is bonded in a 4-coordinate geometry to four equivalent S(1) and four equivalent S(2) atoms. All V(2)-S(1) bond lengths are 2.40 Å. All V(2)-S(2) bond lengths are 3.01 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent V(2) and three equivalent V(1) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent V(2) and four equivalent V(1) atoms.