Cu3V2O8 crystallizes in the monoclinic P2_1/c space group. V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form VO4 tetrahedra that share corners with five equivalent Cu(1)O5 square pyramids. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form distorted CuO5 square pyramids that share corners with two equivalent Cu(1)O5 square pyramids and corners with five equivalent V(1)O4 tetrahedra. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(4) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one Cu(1), and one Cu(2) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Cu(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1) and two equivalent Cu(1) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one Cu(1), and one Cu(2) atom.
Cu3V2O8 crystallizes in the monoclinic P2_1/c space group. V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form VO4 tetrahedra that share corners with five equivalent Cu(1)O5 square pyramids. The V(1)-O(1) bond length is 1.79 Å. The V(1)-O(2) bond length is 1.71 Å. The V(1)-O(3) bond length is 1.73 Å. The V(1)-O(4) bond length is 1.82 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form distorted CuO5 square pyramids that share corners with two equivalent Cu(1)O5 square pyramids and corners with five equivalent V(1)O4 tetrahedra. The Cu(1)-O(1) bond length is 1.99 Å. The Cu(1)-O(2) bond length is 1.92 Å. The Cu(1)-O(4) bond length is 1.97 Å. There is one shorter (1.91 Å) and one longer (2.46 Å) Cu(1)-O(3) bond length. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(4) atoms. Both Cu(2)-O(1) bond lengths are 1.96 Å. Both Cu(2)-O(4) bond lengths are 1.92 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one Cu(1), and one Cu(2) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Cu(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1) and two equivalent Cu(1) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one Cu(1), and one Cu(2) atom.