V5C2P4H4O15F2 crystallizes in the monoclinic C2 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one V(3), one O(14), one O(5), one O(6), one O(7), and one O(8) atom to form distorted VVO5 pentagonal pyramids that share  a cornercorner with one V(4)VO5 pentagonal pyramid,  a cornercorner with one P(1)CO3 tetrahedra,  a cornercorner with one P(2)CO3 tetrahedra,  a cornercorner with one P(3)CO3 tetrahedra, and  a cornercorner with one P(4)CO3 tetrahedra. The V(1)-V(3) bond length is 1.16 Å. The V(1)-O(14) bond length is 2.20 Å. The V(1)-O(5) bond length is 1.97 Å. The V(1)-O(6) bond length is 2.00 Å. The V(1)-O(7) bond length is 1.99 Å. The V(1)-O(8) bond length is 1.98 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one V(4), one O(10), one O(11), one O(13), one O(2), and one O(3) atom. The V(2)-V(4) bond length is 1.16 Å. The V(2)-O(10) bond length is 1.97 Å. The V(2)-O(11) bond length is 1.99 Å. The V(2)-O(13) bond length is 1.59 Å. The V(2)-O(2) bond length is 1.98 Å. The V(2)-O(3) bond length is 1.97 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one V(1), one O(15), one O(5), one O(6), one O(7), and one O(8) atom. The V(3)-O(15) bond length is 1.65 Å. The V(3)-O(5) bond length is 2.03 Å. The V(3)-O(6) bond length is 1.99 Å. The V(3)-O(7) bond length is 1.97 Å. The V(3)-O(8) bond length is 2.05 Å. In the fourth V site, V(4) is bonded to one V(2), one O(10), one O(11), one O(14), one O(2), and one O(3) atom to form distorted VVO5 pentagonal pyramids that share  a cornercorner with one V(1)VO5 pentagonal pyramid,  a cornercorner with one P(1)CO3 tetrahedra,  a cornercorner with one P(2)CO3 tetrahedra,  a cornercorner with one P(3)CO3 tetrahedra, and  a cornercorner with one P(4)CO3 tetrahedra. The V(4)-O(10) bond length is 1.97 Å. The V(4)-O(11) bond length is 2.01 Å. The V(4)-O(14) bond length is 1.60 Å. The V(4)-O(2) bond length is 2.00 Å. The V(4)-O(3) bond length is 2.01 Å. In the fifth V site, V(5) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent F(1) atoms. Both V(5)-O(1) bond lengths are 2.02 Å. Both V(5)-F(1) bond lengths are 1.94 Å. In the sixth V site, V(6) is bonded in a square co-planar geometry to two equivalent O(12) and two equivalent F(2) atoms. Both V(6)-O(12) bond lengths are 2.02 Å. Both V(6)-F(2) bond lengths are 1.94 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a distorted tetrahedral geometry to one P(1); one P(3); and two equivalent H(1,2) atoms. The C(1)-P(1) bond length is 1.79 Å. The C(1)-P(3) bond length is 1.82 Å. Both C(1)-H(1,2) bond lengths are 0.97 Å. In the second C site, C(2) is bonded in a distorted tetrahedral geometry to one P(2); one P(4); and two equivalent H(3,4) atoms. The C(2)-P(2) bond length is 1.80 Å. The C(2)-P(4) bond length is 1.81 Å. Both C(2)-H(3,4) bond lengths are 0.97 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one C(1), one O(1), one O(2), and one O(6) atom to form PCO3 tetrahedra that share  a cornercorner with one V(1)VO5 pentagonal pyramid,  a cornercorner with one V(4)VO5 pentagonal pyramid, and  a cornercorner with one P(3)CO3 tetrahedra. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(6) bond length is 1.54 Å. In the second P site, P(2) is bonded to one C(2), one O(11), one O(12), and one O(8) atom to form PCO3 tetrahedra that share  a cornercorner with one V(1)VO5 pentagonal pyramid,  a cornercorner with one V(4)VO5 pentagonal pyramid, and  a cornercorner with one P(4)CO3 tetrahedra. The P(2)-O(11) bond length is 1.54 Å. The P(2)-O(12) bond length is 1.51 Å. The P(2)-O(8) bond length is 1.54 Å. In the third P site, P(3) is bonded to one C(1), one O(3), one O(4), and one O(5) atom to form PCO3 tetrahedra that share  a cornercorner with one V(1)VO5 pentagonal pyramid,  a cornercorner with one V(4)VO5 pentagonal pyramid, and  a cornercorner with one P(1)CO3 tetrahedra. The P(3)-O(3) bond length is 1.54 Å. The P(3)-O(4) bond length is 1.50 Å. The P(3)-O(5) bond length is 1.55 Å. In the fourth P site, P(4) is bonded to one C(2), one O(10), one O(7), and one O(9) atom to form distorted PCO3 tetrahedra that share  a cornercorner with one V(1)VO5 pentagonal pyramid,  a cornercorner with one V(4)VO5 pentagonal pyramid, and  a cornercorner with one P(2)CO3 tetrahedra. The P(4)-O(10) bond length is 1.54 Å. The P(4)-O(7) bond length is 1.54 Å. The P(4)-O(9) bond length is 1.50 Å. There are two inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(3,4) is bonded in a single-bond geometry to one C(2) atom. There are fifteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(5) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(2), one V(4), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(2), one V(4), and one P(3) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one P(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(4) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(2) atom. In the ninth O site, O(9) is bonded in a single-bond geometry to one P(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one V(2), one V(4), and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one V(2), one V(4), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one V(6) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a single-bond geometry to one V(2) atom. In the fourteenth O site, O(14) is bonded in a 1-coordinate geometry to one V(1) and one V(4) atom. In the fifteenth O site, O(15) is bonded in a single-bond geometry to one V(3) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one V(5) atom. In the second F site, F(2) is bonded in a single-bond geometry to one V(6) atom. Linkers: 8 [O]P([O])(=O)CP([O])([O])=O. Metal clusters: 20 [V]. The MOF has largest included sphere 4.88 A, density 1.64 g/cm3, surface area 2683.97 m2/g, accessible volume 0.31 cm3/g