V4P7(HO3)7 crystallizes in the trigonal P-3c1 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form VO5 square pyramids that share  a cornercorner with one P(1)HO3 tetrahedra,  a cornercorner with one P(3)HO3 tetrahedra, and corners with three equivalent P(2)HO3 tetrahedra. The V(1)-O(1) bond length is 2.00 Å. The V(1)-O(2) bond length is 2.00 Å. The V(1)-O(3) bond length is 1.97 Å. The V(1)-O(4) bond length is 2.00 Å. The V(1)-O(5) bond length is 1.96 Å. In the second V site, V(2) is bonded to six equivalent O(6) atoms to form VO6 octahedra that share corners with six equivalent P(1)HO3 tetrahedra. All V(2)-O(6) bond lengths are 2.01 Å. In the third V site, V(3) is bonded to six equivalent O(7) atoms to form VO6 octahedra that share corners with six equivalent P(1)HO3 tetrahedra. All V(3)-O(7) bond lengths are 2.01 Å. There are three inequivalent P sites. In the first P site, P(3) is bonded to one H(3) and three equivalent O(5) atoms to form distorted PHO3 tetrahedra that share corners with three equivalent V(1)O5 square pyramids. The P(3)-H(3) bond length is 1.32 Å. All P(3)-O(5) bond lengths are 1.53 Å. In the second P site, P(1) is bonded to one H(1), one O(1), one O(6), and one O(7) atom to form distorted PHO3 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 39-47°. The P(1)-H(1) bond length is 1.41 Å. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(6) bond length is 1.53 Å. The P(1)-O(7) bond length is 1.52 Å. In the third P site, P(2) is bonded to one H(2), one O(2), one O(3), and one O(4) atom to form distorted PHO3 tetrahedra that share corners with three equivalent V(1)O5 square pyramids. The P(2)-H(2) bond length is 1.44 Å. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(3) bond length is 1.51 Å. The P(2)-O(4) bond length is 1.52 Å. There are three inequivalent H sites. In the first H site, H(3) is bonded in a single-bond geometry to one P(3) atom. In the second H site, H(1) is bonded in a single-bond geometry to one P(1) atom. In the third H site, H(2) is bonded in a single-bond geometry to one P(2) atom. There are seven 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 distorted bent 120 degrees geometry to one V(1) and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one V(3) and one P(1) atom. Linkers: 28 [O][PH]([O])=O. Metal clusters: 16 [V]. The MOF has largest included sphere 5.04 A, density 1.76 g/cm3, surface area 2956.94 m2/g, accessible volume 0.27 cm3/g