V3P4H4(O6F)2 crystallizes in the orthorhombic Pbca space group. There are two 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 F(1) atom to form VO4F square pyramids that share  a cornercorner with one V(2)O4F2 octahedra, corners with two equivalent P(1)HO3 tetrahedra, and corners with two equivalent P(2)HO3 tetrahedra. The corner-sharing octahedral tilt angles are 44°. The V(1)-O(1) bond length is 2.00 Å. The V(1)-O(2) bond length is 2.02 Å. The V(1)-O(3) bond length is 2.00 Å. The V(1)-O(4) bond length is 2.01 Å. The V(1)-F(1) bond length is 2.22 Å. In the second V site, V(2) is bonded to two equivalent O(5), two equivalent O(6), and two equivalent F(1) atoms to form VO4F2 octahedra that share corners with two equivalent V(1)O4F square pyramids, corners with two equivalent P(1)HO3 tetrahedra, and corners with two equivalent P(2)HO3 tetrahedra. Both V(2)-O(5) bond lengths are 1.98 Å. Both V(2)-O(6) bond lengths are 2.02 Å. Both V(2)-F(1) bond lengths are 1.88 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one H(1), one O(1), one O(3), and one O(5) atom to form distorted PHO3 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra and corners with two equivalent V(1)O4F square pyramids. The corner-sharing octahedral tilt angles are 41°. The P(1)-H(1) bond length is 1.30 Å. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(5) bond length is 1.51 Å. In the second P site, P(2) is bonded to one H(2), one O(2), one O(4), and one O(6) atom to form PHO3 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra and corners with two equivalent V(1)O4F square pyramids. The corner-sharing octahedral tilt angles are 53°. The P(2)-H(2) bond length is 1.31 Å. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(4) bond length is 1.50 Å. The P(2)-O(6) bond length is 1.54 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one P(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one P(2) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 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(1) atom. In the fourth O site, O(4) is bonded in a 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(2) and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one V(2) and one P(2) atom. F(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(2) atom. Linkers: 16 [O][PH]([O])=O. Metal clusters: 12 [V]. The MOF has largest included sphere 4.03 A, density 1.86 g/cm3, surface area 2901.32 m2/g, accessible volume 0.24 cm3/g