V2C4P2H4O11 crystallizes in the orthorhombic Pnna space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(5) atoms. Both V(1)-O(1) bond lengths are 2.00 Å. Both V(1)-O(5) bond lengths are 2.01 Å. In the second V site, V(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra and corners with four equivalent P(1)CO3 tetrahedra. The corner-sharing octahedral tilt angles are 45°. Both V(2)-O(2) bond lengths are 1.98 Å. Both V(2)-O(3) bond lengths are 1.99 Å. Both V(2)-O(6) bond lengths are 1.91 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one O(4) and one O(5) atom. The C(1)-O(4) bond length is 1.21 Å. The C(1)-O(5) bond length is 1.28 Å. In the second C site, C(2) is bonded in a distorted water-like geometry to one P(1) and two equivalent H(1,2) atoms. The C(2)-P(1) bond length is 1.80 Å. Both C(2)-H(1,2) bond lengths are 0.97 Å. P(1) is bonded to one C(2), one O(1), one O(2), and one O(3) atom to form PCO3 tetrahedra that share corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.52 Å. H(1,2) is bonded in a single-bond geometry to one C(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(2) and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one C(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one V(1) and one C(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to two equivalent V(2) atoms. Linkers: 8 [O]C(=O)CP([O])([O])=O. Metal clusters: 8 [V]. The MOF has largest included sphere 5.59 A, density 1.36 g/cm3, surface area 3357.18 m2/g, accessible volume 0.36 cm3/g