V3(PO5)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 square co-planar geometry to one O(1), one O(2), one O(3), and one O(5) atom. The V(1)-O(1) bond length is 1.97 Å. The V(1)-O(2) bond length is 2.03 Å. The V(1)-O(3) bond length is 2.00 Å. The V(1)-O(5) bond length is 1.90 Å. In the second V site, V(2) is bonded in a distorted square co-planar geometry to two equivalent O(4) and two equivalent O(5) atoms. Both V(2)-O(4) bond lengths are 1.96 Å. Both V(2)-O(5) bond lengths are 1.90 Å. P(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(4) atom. The P(1)-O(1) bond length is 1.55 Å. 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. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one V(2) and one P(1) atom. In the fifth O site, O(5) is bonded in a 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 4.50 A, density 1.65 g/cm3, surface area 2647.94 m2/g, accessible volume 0.28 cm3/g