V4Cu3S8 crystallizes in the trigonal R3m space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form edge-sharing VS6 octahedra. In the second V site, V(2) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form distorted edge-sharing VS6 octahedra. Cu(1) is bonded in a rectangular see-saw-like geometry to one S(1), one S(3), and two equivalent S(2) atoms. There are four inequivalent S sites. In the first S site, S(1) is bonded to one V(1), two equivalent V(2), and one Cu(1) atom to form corner-sharing SV3Cu trigonal pyramids. In the second S site, S(2) is bonded in a distorted pentagonal planar geometry to one V(1), two equivalent V(2), and two equivalent Cu(1) atoms. In the third S site, S(3) is bonded in a 6-coordinate geometry to three equivalent V(2) and three equivalent Cu(1) atoms. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to three equivalent V(2) atoms.
V4Cu3S8 crystallizes in the trigonal R3m space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form edge-sharing VS6 octahedra. All V(1)-S(1) bond lengths are 2.35 Å. All V(1)-S(2) bond lengths are 2.43 Å. In the second V site, V(2) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form distorted edge-sharing VS6 octahedra. The V(2)-S(3) bond length is 2.52 Å. The V(2)-S(4) bond length is 2.28 Å. Both V(2)-S(1) bond lengths are 2.47 Å. Both V(2)-S(2) bond lengths are 2.36 Å. Cu(1) is bonded in a rectangular see-saw-like geometry to one S(1), one S(3), and two equivalent S(2) atoms. The Cu(1)-S(1) bond length is 2.22 Å. The Cu(1)-S(3) bond length is 2.32 Å. Both Cu(1)-S(2) bond lengths are 2.36 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one V(1), two equivalent V(2), and one Cu(1) atom to form corner-sharing SV3Cu trigonal pyramids. In the second S site, S(2) is bonded in a distorted pentagonal planar geometry to one V(1), two equivalent V(2), and two equivalent Cu(1) atoms. In the third S site, S(3) is bonded in a 6-coordinate geometry to three equivalent V(2) and three equivalent Cu(1) atoms. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to three equivalent V(2) atoms.