VCu3(SeS)2 is Sulvanite-derived structured and crystallizes in the orthorhombic Cmm2 space group. V(1) is bonded to two equivalent Se(1) and two equivalent S(1) atoms to form VSe2S2 tetrahedra that share edges with two equivalent Cu(2)Se2S2 tetrahedra and edges with four equivalent Cu(1)Se2S2 tetrahedra. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent Se(1) and two equivalent S(1) atoms to form distorted CuSe2S2 tetrahedra that share corners with four equivalent Cu(1)Se2S2 tetrahedra, corners with four equivalent Cu(2)Se2S2 tetrahedra, and edges with two equivalent V(1)Se2S2 tetrahedra. In the second Cu site, Cu(2) is bonded to two equivalent Se(1) and two equivalent S(1) atoms to form distorted CuSe2S2 tetrahedra that share corners with eight equivalent Cu(1)Se2S2 tetrahedra and edges with two equivalent V(1)Se2S2 tetrahedra. Se(1) is bonded to one V(1), one Cu(2), and two equivalent Cu(1) atoms to form SeVCu3 tetrahedra that share corners with two equivalent Se(1)VCu3 tetrahedra, corners with four equivalent S(1)VCu3 tetrahedra,  an edgeedge with one Se(1)VCu3 tetrahedra, and edges with two equivalent S(1)VCu3 tetrahedra. S(1) is bonded to one V(1), one Cu(2), and two equivalent Cu(1) atoms to form distorted SVCu3 tetrahedra that share corners with two equivalent S(1)VCu3 tetrahedra, corners with four equivalent Se(1)VCu3 tetrahedra,  an edgeedge with one S(1)VCu3 tetrahedra, and edges with two equivalent Se(1)VCu3 tetrahedra.
VCu3(SeS)2 is Sulvanite-derived structured and crystallizes in the orthorhombic Cmm2 space group. V(1) is bonded to two equivalent Se(1) and two equivalent S(1) atoms to form VSe2S2 tetrahedra that share edges with two equivalent Cu(2)Se2S2 tetrahedra and edges with four equivalent Cu(1)Se2S2 tetrahedra. Both V(1)-Se(1) bond lengths are 2.35 Å. Both V(1)-S(1) bond lengths are 2.22 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent Se(1) and two equivalent S(1) atoms to form distorted CuSe2S2 tetrahedra that share corners with four equivalent Cu(1)Se2S2 tetrahedra, corners with four equivalent Cu(2)Se2S2 tetrahedra, and edges with two equivalent V(1)Se2S2 tetrahedra. Both Cu(1)-Se(1) bond lengths are 2.43 Å. Both Cu(1)-S(1) bond lengths are 2.28 Å. In the second Cu site, Cu(2) is bonded to two equivalent Se(1) and two equivalent S(1) atoms to form distorted CuSe2S2 tetrahedra that share corners with eight equivalent Cu(1)Se2S2 tetrahedra and edges with two equivalent V(1)Se2S2 tetrahedra. Both Cu(2)-Se(1) bond lengths are 2.41 Å. Both Cu(2)-S(1) bond lengths are 2.30 Å. Se(1) is bonded to one V(1), one Cu(2), and two equivalent Cu(1) atoms to form SeVCu3 tetrahedra that share corners with two equivalent Se(1)VCu3 tetrahedra, corners with four equivalent S(1)VCu3 tetrahedra,  an edgeedge with one Se(1)VCu3 tetrahedra, and edges with two equivalent S(1)VCu3 tetrahedra. S(1) is bonded to one V(1), one Cu(2), and two equivalent Cu(1) atoms to form distorted SVCu3 tetrahedra that share corners with two equivalent S(1)VCu3 tetrahedra, corners with four equivalent Se(1)VCu3 tetrahedra,  an edgeedge with one S(1)VCu3 tetrahedra, and edges with two equivalent Se(1)VCu3 tetrahedra.