V2(CuO3)3 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(6), and two equivalent O(2) atoms to form VO4 tetrahedra that share  a cornercorner with one Cu(2)O5 square pyramid,  a cornercorner with one V(2)O4 tetrahedra, and corners with three equivalent Cu(3)O5 trigonal bipyramids. In the second V site, V(2) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form VO4 tetrahedra that share corners with two equivalent Cu(2)O5 square pyramids,  a cornercorner with one V(1)O4 tetrahedra, and  a cornercorner with one Cu(3)O5 trigonal bipyramid. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. In the second Cu site, Cu(2) is bonded to one O(1), one O(3), one O(7), and two equivalent O(4) atoms to form distorted CuO5 square pyramids that share  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and  an edgeedge with one Cu(3)O5 trigonal bipyramid. In the third Cu site, Cu(3) is bonded to one O(1), one O(3), one O(5), and two equivalent O(2) atoms to form distorted CuO5 trigonal bipyramids that share  a cornercorner with one V(2)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, and  an edgeedge with one Cu(2)O5 square pyramid. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Cu(2), one Cu(3), and two equivalent Cu(1) atoms to form corner-sharing OCu4 tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one Cu(1), and one Cu(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1), one Cu(2), and one Cu(3) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(2) and one Cu(2) atom. In the fifth O site, O(5) is bonded in a linear geometry to one V(2) and one Cu(3) atom. In the sixth O site, O(6) is bonded in a linear geometry to one V(1) and one V(2) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one Cu(2) atom.
V2(CuO3)3 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(6), and two equivalent O(2) atoms to form VO4 tetrahedra that share  a cornercorner with one Cu(2)O5 square pyramid,  a cornercorner with one V(2)O4 tetrahedra, and corners with three equivalent Cu(3)O5 trigonal bipyramids. The V(1)-O(3) bond length is 1.67 Å. The V(1)-O(6) bond length is 1.79 Å. Both V(1)-O(2) bond lengths are 1.77 Å. In the second V site, V(2) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form VO4 tetrahedra that share corners with two equivalent Cu(2)O5 square pyramids,  a cornercorner with one V(1)O4 tetrahedra, and  a cornercorner with one Cu(3)O5 trigonal bipyramid. The V(2)-O(5) bond length is 1.70 Å. The V(2)-O(6) bond length is 1.79 Å. Both V(2)-O(4) bond lengths are 1.75 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Cu(1)-O(1) bond lengths are 1.89 Å. Both Cu(1)-O(2) bond lengths are 1.94 Å. In the second Cu site, Cu(2) is bonded to one O(1), one O(3), one O(7), and two equivalent O(4) atoms to form distorted CuO5 square pyramids that share  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and  an edgeedge with one Cu(3)O5 trigonal bipyramid. The Cu(2)-O(1) bond length is 1.91 Å. The Cu(2)-O(3) bond length is 2.40 Å. The Cu(2)-O(7) bond length is 1.77 Å. Both Cu(2)-O(4) bond lengths are 1.88 Å. In the third Cu site, Cu(3) is bonded to one O(1), one O(3), one O(5), and two equivalent O(2) atoms to form distorted CuO5 trigonal bipyramids that share  a cornercorner with one V(2)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, and  an edgeedge with one Cu(2)O5 square pyramid. The Cu(3)-O(1) bond length is 2.02 Å. The Cu(3)-O(3) bond length is 2.22 Å. The Cu(3)-O(5) bond length is 1.88 Å. Both Cu(3)-O(2) bond lengths are 2.00 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Cu(2), one Cu(3), and two equivalent Cu(1) atoms to form corner-sharing OCu4 tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one Cu(1), and one Cu(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1), one Cu(2), and one Cu(3) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(2) and one Cu(2) atom. In the fifth O site, O(5) is bonded in a linear geometry to one V(2) and one Cu(3) atom. In the sixth O site, O(6) is bonded in a linear geometry to one V(1) and one V(2) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one Cu(2) atom.