Na2VCu3S4 crystallizes in the monoclinic Cm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form distorted NaS6 octahedra that share  a cornercorner with one V(1)S4 tetrahedra,  a cornercorner with one Cu(2)S4 tetrahedra, corners with five equivalent Cu(1)S4 tetrahedra, corners with five equivalent Cu(3)S4 tetrahedra, edges with two equivalent Na(1)S6 octahedra, edges with four equivalent Na(2)S6 octahedra,  an edgeedge with one Cu(1)S4 tetrahedra,  an edgeedge with one Cu(3)S4 tetrahedra, edges with two equivalent V(1)S4 tetrahedra, and edges with two equivalent Cu(2)S4 tetrahedra. In the second Na site, Na(2) is bonded to one S(1), one S(3), two equivalent S(2), and two equivalent S(4) atoms to form distorted NaS6 octahedra that share  a cornercorner with one Cu(1)S4 tetrahedra,  a cornercorner with one Cu(3)S4 tetrahedra, corners with five equivalent V(1)S4 tetrahedra, corners with five equivalent Cu(2)S4 tetrahedra, edges with two equivalent Na(2)S6 octahedra, edges with four equivalent Na(1)S6 octahedra,  an edgeedge with one V(1)S4 tetrahedra,  an edgeedge with one Cu(2)S4 tetrahedra, edges with two equivalent Cu(1)S4 tetrahedra, and edges with two equivalent Cu(3)S4 tetrahedra. V(1) is bonded to one S(1), one S(4), and two equivalent S(2) atoms to form VS4 tetrahedra that share  a cornercorner with one Na(1)S6 octahedra, corners with five equivalent Na(2)S6 octahedra, corners with two equivalent V(1)S4 tetrahedra, corners with four equivalent Cu(1)S4 tetrahedra,  an edgeedge with one Na(2)S6 octahedra, edges with two equivalent Na(1)S6 octahedra,  an edgeedge with one Cu(3)S4 tetrahedra, and edges with two equivalent Cu(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 21-50°. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form CuS4 tetrahedra that share  a cornercorner with one Na(2)S6 octahedra, corners with five equivalent Na(1)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, corners with four equivalent V(1)S4 tetrahedra,  an edgeedge with one Na(1)S6 octahedra, edges with two equivalent Na(2)S6 octahedra,  an edgeedge with one Cu(2)S4 tetrahedra, and edges with two equivalent Cu(3)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-54°. In the second Cu site, Cu(2) is bonded to one S(2), one S(3), and two equivalent S(4) atoms to form distorted CuS4 tetrahedra that share  a cornercorner with one Na(1)S6 octahedra, corners with five equivalent Na(2)S6 octahedra, corners with two equivalent Cu(2)S4 tetrahedra, corners with four equivalent Cu(3)S4 tetrahedra,  an edgeedge with one Na(2)S6 octahedra, edges with two equivalent Na(1)S6 octahedra,  an edgeedge with one Cu(1)S4 tetrahedra, and edges with two equivalent V(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 17-50°. In the third Cu site, Cu(3) is bonded to one S(1), one S(4), and two equivalent S(3) atoms to form distorted CuS4 tetrahedra that share  a cornercorner with one Na(2)S6 octahedra, corners with five equivalent Na(1)S6 octahedra, corners with two equivalent Cu(3)S4 tetrahedra, corners with four equivalent Cu(2)S4 tetrahedra,  an edgeedge with one Na(1)S6 octahedra, edges with two equivalent Na(2)S6 octahedra,  an edgeedge with one V(1)S4 tetrahedra, and edges with two equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-52°. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 7-coordinate geometry to one Na(2), two equivalent Na(1), one V(1), one Cu(3), and two equivalent Cu(1) atoms. In the second S site, S(2) is bonded in a 7-coordinate geometry to one Na(1), two equivalent Na(2), two equivalent V(1), one Cu(1), and one Cu(2) atom. In the third S site, S(3) is bonded to one Na(2), two equivalent Na(1), one Cu(1), one Cu(2), and two equivalent Cu(3) atoms to form distorted edge-sharing SNa3Cu4 pentagonal bipyramids. In the fourth S site, S(4) is bonded in a 7-coordinate geometry to one Na(1), two equivalent Na(2), one V(1), one Cu(3), and two equivalent Cu(2) atoms.
Na2VCu3S4 crystallizes in the monoclinic Cm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form distorted NaS6 octahedra that share  a cornercorner with one V(1)S4 tetrahedra,  a cornercorner with one Cu(2)S4 tetrahedra, corners with five equivalent Cu(1)S4 tetrahedra, corners with five equivalent Cu(3)S4 tetrahedra, edges with two equivalent Na(1)S6 octahedra, edges with four equivalent Na(2)S6 octahedra,  an edgeedge with one Cu(1)S4 tetrahedra,  an edgeedge with one Cu(3)S4 tetrahedra, edges with two equivalent V(1)S4 tetrahedra, and edges with two equivalent Cu(2)S4 tetrahedra. The Na(1)-S(2) bond length is 2.98 Å. The Na(1)-S(4) bond length is 2.90 Å. Both Na(1)-S(1) bond lengths are 2.93 Å. Both Na(1)-S(3) bond lengths are 2.80 Å. In the second Na site, Na(2) is bonded to one S(1), one S(3), two equivalent S(2), and two equivalent S(4) atoms to form distorted NaS6 octahedra that share  a cornercorner with one Cu(1)S4 tetrahedra,  a cornercorner with one Cu(3)S4 tetrahedra, corners with five equivalent V(1)S4 tetrahedra, corners with five equivalent Cu(2)S4 tetrahedra, edges with two equivalent Na(2)S6 octahedra, edges with four equivalent Na(1)S6 octahedra,  an edgeedge with one V(1)S4 tetrahedra,  an edgeedge with one Cu(2)S4 tetrahedra, edges with two equivalent Cu(1)S4 tetrahedra, and edges with two equivalent Cu(3)S4 tetrahedra. The Na(2)-S(1) bond length is 2.91 Å. The Na(2)-S(3) bond length is 2.79 Å. Both Na(2)-S(2) bond lengths are 2.97 Å. Both Na(2)-S(4) bond lengths are 2.91 Å. V(1) is bonded to one S(1), one S(4), and two equivalent S(2) atoms to form VS4 tetrahedra that share  a cornercorner with one Na(1)S6 octahedra, corners with five equivalent Na(2)S6 octahedra, corners with two equivalent V(1)S4 tetrahedra, corners with four equivalent Cu(1)S4 tetrahedra,  an edgeedge with one Na(2)S6 octahedra, edges with two equivalent Na(1)S6 octahedra,  an edgeedge with one Cu(3)S4 tetrahedra, and edges with two equivalent Cu(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 21-50°. The V(1)-S(1) bond length is 2.32 Å. The V(1)-S(4) bond length is 2.29 Å. Both V(1)-S(2) bond lengths are 2.36 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form CuS4 tetrahedra that share  a cornercorner with one Na(2)S6 octahedra, corners with five equivalent Na(1)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, corners with four equivalent V(1)S4 tetrahedra,  an edgeedge with one Na(1)S6 octahedra, edges with two equivalent Na(2)S6 octahedra,  an edgeedge with one Cu(2)S4 tetrahedra, and edges with two equivalent Cu(3)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-54°. The Cu(1)-S(2) bond length is 2.41 Å. The Cu(1)-S(3) bond length is 2.41 Å. Both Cu(1)-S(1) bond lengths are 2.37 Å. In the second Cu site, Cu(2) is bonded to one S(2), one S(3), and two equivalent S(4) atoms to form distorted CuS4 tetrahedra that share  a cornercorner with one Na(1)S6 octahedra, corners with five equivalent Na(2)S6 octahedra, corners with two equivalent Cu(2)S4 tetrahedra, corners with four equivalent Cu(3)S4 tetrahedra,  an edgeedge with one Na(2)S6 octahedra, edges with two equivalent Na(1)S6 octahedra,  an edgeedge with one Cu(1)S4 tetrahedra, and edges with two equivalent V(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 17-50°. The Cu(2)-S(2) bond length is 2.41 Å. The Cu(2)-S(3) bond length is 2.30 Å. Both Cu(2)-S(4) bond lengths are 2.36 Å. In the third Cu site, Cu(3) is bonded to one S(1), one S(4), and two equivalent S(3) atoms to form distorted CuS4 tetrahedra that share  a cornercorner with one Na(2)S6 octahedra, corners with five equivalent Na(1)S6 octahedra, corners with two equivalent Cu(3)S4 tetrahedra, corners with four equivalent Cu(2)S4 tetrahedra,  an edgeedge with one Na(1)S6 octahedra, edges with two equivalent Na(2)S6 octahedra,  an edgeedge with one V(1)S4 tetrahedra, and edges with two equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-52°. The Cu(3)-S(1) bond length is 2.45 Å. The Cu(3)-S(4) bond length is 2.36 Å. Both Cu(3)-S(3) bond lengths are 2.33 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 7-coordinate geometry to one Na(2), two equivalent Na(1), one V(1), one Cu(3), and two equivalent Cu(1) atoms. In the second S site, S(2) is bonded in a 7-coordinate geometry to one Na(1), two equivalent Na(2), two equivalent V(1), one Cu(1), and one Cu(2) atom. In the third S site, S(3) is bonded to one Na(2), two equivalent Na(1), one Cu(1), one Cu(2), and two equivalent Cu(3) atoms to form distorted edge-sharing SNa3Cu4 pentagonal bipyramids. In the fourth S site, S(4) is bonded in a 7-coordinate geometry to one Na(1), two equivalent Na(2), one V(1), one Cu(3), and two equivalent Cu(2) atoms.