V2Cu5(HO3)4 crystallizes in the triclinic P-1 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  a cornercorner with one Cu(2)O6 octahedra, corners with four equivalent Cu(1)O6 octahedra, and corners with four equivalent Cu(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-61°. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(2), one O(4), one O(5), one O(6), and two equivalent O(3) atoms to form distorted CuO6 octahedra that share corners with four equivalent V(1)O4 tetrahedra,  an edgeedge with one Cu(1)O6 octahedra,  an edgeedge with one Cu(2)O6 octahedra, and edges with two equivalent Cu(3)O6 octahedra. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form distorted CuO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, edges with two equivalent Cu(1)O6 octahedra, and edges with four equivalent Cu(3)O6 octahedra. In the third Cu site, Cu(3) is bonded to one O(2), one O(4), one O(5), one O(6), and two equivalent O(1) atoms to form CuO6 octahedra that share corners with four equivalent V(1)O4 tetrahedra,  an edgeedge with one Cu(3)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and edges with two equivalent Cu(2)O6 octahedra. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(6) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(5) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one V(1), one Cu(2), and two equivalent Cu(3) atoms. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(1), one Cu(1), and one Cu(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Cu(1) atoms. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one V(1), one Cu(1), and one Cu(3) atom. In the fifth O site, O(5) is bonded to one Cu(1), one Cu(2), one Cu(3), and one H(2) atom to form distorted corner-sharing OCu3H tetrahedra. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Cu(1), one Cu(2), one Cu(3), and one H(1) atom.
V2Cu5(HO3)4 crystallizes in the triclinic P-1 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  a cornercorner with one Cu(2)O6 octahedra, corners with four equivalent Cu(1)O6 octahedra, and corners with four equivalent Cu(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-61°. The V(1)-O(1) bond length is 1.76 Å. The V(1)-O(2) bond length is 1.77 Å. The V(1)-O(3) bond length is 1.80 Å. The V(1)-O(4) bond length is 1.70 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(2), one O(4), one O(5), one O(6), and two equivalent O(3) atoms to form distorted CuO6 octahedra that share corners with four equivalent V(1)O4 tetrahedra,  an edgeedge with one Cu(1)O6 octahedra,  an edgeedge with one Cu(2)O6 octahedra, and edges with two equivalent Cu(3)O6 octahedra. The Cu(1)-O(2) bond length is 2.54 Å. The Cu(1)-O(4) bond length is 2.60 Å. The Cu(1)-O(5) bond length is 1.97 Å. The Cu(1)-O(6) bond length is 2.01 Å. There is one shorter (1.94 Å) and one longer (1.95 Å) Cu(1)-O(3) bond length. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form distorted CuO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, edges with two equivalent Cu(1)O6 octahedra, and edges with four equivalent Cu(3)O6 octahedra. Both Cu(2)-O(1) bond lengths are 2.51 Å. Both Cu(2)-O(5) bond lengths are 2.00 Å. Both Cu(2)-O(6) bond lengths are 2.00 Å. In the third Cu site, Cu(3) is bonded to one O(2), one O(4), one O(5), one O(6), and two equivalent O(1) atoms to form CuO6 octahedra that share corners with four equivalent V(1)O4 tetrahedra,  an edgeedge with one Cu(3)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and edges with two equivalent Cu(2)O6 octahedra. The Cu(3)-O(2) bond length is 1.96 Å. The Cu(3)-O(4) bond length is 2.38 Å. The Cu(3)-O(5) bond length is 2.03 Å. The Cu(3)-O(6) bond length is 2.03 Å. There is one shorter (1.96 Å) and one longer (2.37 Å) Cu(3)-O(1) bond length. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(6) atom. The H(1)-O(6) bond length is 1.00 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(5) atom. The H(2)-O(5) bond length is 1.00 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one V(1), one Cu(2), and two equivalent Cu(3) atoms. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(1), one Cu(1), and one Cu(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Cu(1) atoms. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one V(1), one Cu(1), and one Cu(3) atom. In the fifth O site, O(5) is bonded to one Cu(1), one Cu(2), one Cu(3), and one H(2) atom to form distorted corner-sharing OCu3H tetrahedra. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Cu(1), one Cu(2), one Cu(3), and one H(1) atom.