V3P2(HO5)2 crystallizes in the orthorhombic Pnma space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. The V(1)-O(1) bond length is 1.95 Å. The V(1)-O(2) bond length is 2.02 Å. The V(1)-O(3) bond length is 1.99 Å. The V(1)-O(5) bond length is 2.00 Å. In the second V site, V(2) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(4) atoms. Both V(2)-O(1) bond lengths are 1.96 Å. Both V(2)-O(4) bond lengths are 1.96 Å. P(1) is bonded in a tetrahedral geometry to one O(2), one O(3), one O(4), and one O(5) atom. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.54 Å. H(1) is bonded in a single-bond geometry to one O(1) atom. The H(1)-O(1) bond length is 0.74 Å. There are five inequivalent O sites. In the first O site, O(5) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(1) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one H(1) atom. In the third O site, O(2) is bonded in a 2-coordinate geometry to one V(1) and one P(1) atom. In the fourth O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the fifth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one V(2) and one P(1) atom. Linkers: 8 [O]P([O])([O])=O ,8 [OH]. Metal clusters: 12 [V]. The MOF has largest included sphere 4.55 A, density 1.65 g/cm3, surface area 2643.39 m2/g, accessible volume 0.27 cm3/g