V3(HO2)4 crystallizes in the monoclinic Cm space group. There are three inequivalent V sites. In the first V site, V(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. In the second V site, V(2) is bonded to one O(3), one O(5), one O(7), and two equivalent O(8) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. In the third V site, V(3) is bonded to one O(4), one O(6), one O(8), and two equivalent O(7) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. There are four inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to one O(1) and one O(5) atom. In the second H site, H(2) is bonded in a distorted linear geometry to one O(1) and one O(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one O(5) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(6) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one H(1), and one H(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one H(2) atom. In the third O site, O(3) is bonded in a distorted linear geometry to one V(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a linear geometry to one V(1) and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(2), one H(1), and one H(3) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(3) and one H(4) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(3) atoms. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one V(3) and two equivalent V(2) atoms.
V3(HO2)4 crystallizes in the monoclinic Cm space group. There are three inequivalent V sites. In the first V site, V(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. The V(1)-O(1) bond length is 2.02 Å. The V(1)-O(2) bond length is 1.66 Å. The V(1)-O(3) bond length is 2.02 Å. The V(1)-O(4) bond length is 1.83 Å. In the second V site, V(2) is bonded to one O(3), one O(5), one O(7), and two equivalent O(8) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. The V(2)-O(3) bond length is 1.70 Å. The V(2)-O(5) bond length is 1.92 Å. The V(2)-O(7) bond length is 1.96 Å. Both V(2)-O(8) bond lengths are 2.02 Å. In the third V site, V(3) is bonded to one O(4), one O(6), one O(8), and two equivalent O(7) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. The V(3)-O(4) bond length is 1.77 Å. The V(3)-O(6) bond length is 1.77 Å. The V(3)-O(8) bond length is 1.97 Å. Both V(3)-O(7) bond lengths are 1.96 Å. There are four inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to one O(1) and one O(5) atom. The H(1)-O(1) bond length is 1.02 Å. The H(1)-O(5) bond length is 1.55 Å. In the second H site, H(2) is bonded in a distorted linear geometry to one O(1) and one O(2) atom. The H(2)-O(1) bond length is 1.03 Å. The H(2)-O(2) bond length is 1.53 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(5) atom. The H(3)-O(5) bond length is 0.98 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(6) atom. The H(4)-O(6) bond length is 0.99 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one H(1), and one H(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one H(2) atom. In the third O site, O(3) is bonded in a distorted linear geometry to one V(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a linear geometry to one V(1) and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(2), one H(1), and one H(3) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(3) and one H(4) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(3) atoms. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one V(3) and two equivalent V(2) atoms.