V3P2(HO7)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms. The V(1)-O(1) bond length is 1.66 Å. The V(1)-O(3) bond length is 1.94 Å. The V(1)-O(4) bond length is 2.21 Å. The V(1)-O(5) bond length is 1.97 Å. There is one shorter (1.64 Å) and one longer (2.26 Å) V(1)-O(2) bond length. In the second V site, V(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms. Both V(2)-O(1) bond lengths are 2.23 Å. Both V(2)-O(4) bond lengths are 1.64 Å. Both V(2)-O(6) bond lengths are 1.95 Å. P(1) is bonded in a tetrahedral geometry to one O(3), one O(5), one O(6), and one O(7) atom. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(6) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.54 Å. H(1) is bonded in a bent 150 degrees geometry to one H(1) and one O(7) atom. The H(1)-H(1) bond length is 0.34 Å. The H(1)-O(7) bond length is 1.06 Å. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a bent 120 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(6) is bonded in a bent 120 degrees geometry to one V(2) and one P(1) atom. In the third O site, O(7) is bonded in a bent 120 degrees geometry to one P(1) and one H(1) atom. In the fourth O site, O(1) is bonded in a distorted bent 120 degrees geometry to one V(1) and one V(2) atom. In the fifth O site, O(2) is bonded in a distorted bent 150 degrees geometry to two equivalent V(1) atoms. In the sixth O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the seventh O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(2) atom. Linkers: 8 [O]P([O])(=O)O. Metal clusters: 12 [V]. The MOF has largest included sphere 4.87 A, density 1.83 g/cm3, surface area 2238.71 m2/g, accessible volume 0.26 cm3/g