V3(CuS2)4 crystallizes in the trigonal R3m space group. V(1) is bonded to one S(1), one S(2), and two equivalent S(4) atoms to form VS4 tetrahedra that share corners with three equivalent Cu(1)S6 octahedra, corners with four equivalent V(1)S4 tetrahedra, and edges with two equivalent Cu(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-52°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to three equivalent S(1) and three equivalent S(4) atoms to form CuS6 octahedra that share corners with nine equivalent V(1)S4 tetrahedra and corners with nine equivalent Cu(2)S4 tetrahedra. In the second Cu site, Cu(2) is bonded to one S(3), one S(4), and two equivalent S(1) atoms to form distorted CuS4 tetrahedra that share corners with three equivalent Cu(1)S6 octahedra, corners with four equivalent Cu(2)S4 tetrahedra, and edges with two equivalent V(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-59°. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one V(1), one Cu(1), and two equivalent Cu(2) atoms. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to three equivalent V(1) atoms. In the third S site, S(3) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Cu(2) atoms. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to two equivalent V(1), one Cu(1), and one Cu(2) atom.
V3(CuS2)4 crystallizes in the trigonal R3m space group. V(1) is bonded to one S(1), one S(2), and two equivalent S(4) atoms to form VS4 tetrahedra that share corners with three equivalent Cu(1)S6 octahedra, corners with four equivalent V(1)S4 tetrahedra, and edges with two equivalent Cu(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-52°. The V(1)-S(1) bond length is 2.19 Å. The V(1)-S(2) bond length is 2.31 Å. Both V(1)-S(4) bond lengths are 2.28 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to three equivalent S(1) and three equivalent S(4) atoms to form CuS6 octahedra that share corners with nine equivalent V(1)S4 tetrahedra and corners with nine equivalent Cu(2)S4 tetrahedra. All Cu(1)-S(1) bond lengths are 2.50 Å. All Cu(1)-S(4) bond lengths are 2.52 Å. In the second Cu site, Cu(2) is bonded to one S(3), one S(4), and two equivalent S(1) atoms to form distorted CuS4 tetrahedra that share corners with three equivalent Cu(1)S6 octahedra, corners with four equivalent Cu(2)S4 tetrahedra, and edges with two equivalent V(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-59°. The Cu(2)-S(3) bond length is 2.23 Å. The Cu(2)-S(4) bond length is 2.34 Å. Both Cu(2)-S(1) bond lengths are 2.32 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one V(1), one Cu(1), and two equivalent Cu(2) atoms. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to three equivalent V(1) atoms. In the third S site, S(3) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Cu(2) atoms. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to two equivalent V(1), one Cu(1), and one Cu(2) atom.