H2V3O8 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), and three equivalent O(1) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(5), one O(6), and two equivalent O(3) atoms. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(4), one O(8), and three equivalent O(7) atoms. There are two inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to one O(5) and one O(6) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(6) atom. There are eight inequivalent O sites. In the first O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the second O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one H(1) atom. In the third O site, O(6) is bonded in a 3-coordinate geometry to one V(2), one H(1), and one H(2) atom. In the fourth O site, O(7) is bonded in a distorted T-shaped geometry to three equivalent V(3) atoms. In the fifth O site, O(8) is bonded in a single-bond geometry to one V(3) atom. In the sixth O site, O(1) is bonded to one V(2) and three equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing OV4 trigonal pyramids. In the seventh O site, O(2) is bonded in a single-bond geometry to one V(1) atom. In the eighth O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one V(1) and two equivalent V(2) atoms.
H2V3O8 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), and three equivalent O(1) atoms. The V(1)-O(2) bond length is 1.62 Å. The V(1)-O(3) bond length is 1.92 Å. The V(1)-O(4) bond length is 1.94 Å. There are a spread of V(1)-O(1) bond distances ranging from 1.91-2.39 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(5), one O(6), and two equivalent O(3) atoms. The V(2)-O(1) bond length is 2.25 Å. The V(2)-O(4) bond length is 2.19 Å. The V(2)-O(5) bond length is 1.73 Å. The V(2)-O(6) bond length is 1.91 Å. Both V(2)-O(3) bond lengths are 1.95 Å. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(4), one O(8), and three equivalent O(7) atoms. The V(3)-O(4) bond length is 1.85 Å. The V(3)-O(8) bond length is 1.60 Å. There are a spread of V(3)-O(7) bond distances ranging from 1.92-1.98 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to one O(5) and one O(6) atom. The H(1)-O(5) bond length is 1.06 Å. The H(1)-O(6) bond length is 1.48 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(6) atom. The H(2)-O(6) bond length is 0.98 Å. There are eight inequivalent O sites. In the first O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the second O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one H(1) atom. In the third O site, O(6) is bonded in a 3-coordinate geometry to one V(2), one H(1), and one H(2) atom. In the fourth O site, O(7) is bonded in a distorted T-shaped geometry to three equivalent V(3) atoms. In the fifth O site, O(8) is bonded in a single-bond geometry to one V(3) atom. In the sixth O site, O(1) is bonded to one V(2) and three equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing OV4 trigonal pyramids. In the seventh O site, O(2) is bonded in a single-bond geometry to one V(1) atom. In the eighth O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one V(1) and two equivalent V(2) atoms.