V4Co(PO5)4 crystallizes in the triclinic P-1 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 4-coordinate geometry to one O(3), one O(5), one O(8), and one O(9) atom. The V(1)-O(3) bond length is 2.01 Å. The V(1)-O(5) bond length is 2.06 Å. The V(1)-O(8) bond length is 1.66 Å. The V(1)-O(9) bond length is 1.91 Å. In the second V site, V(2) is bonded to two equivalent O(10), two equivalent O(6), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 45°. Both V(2)-O(10) bond lengths are 1.91 Å. Both V(2)-O(6) bond lengths are 1.98 Å. Both V(2)-O(7) bond lengths are 1.98 Å. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(10), and two equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 45°. Both V(3)-O(1) bond lengths are 1.98 Å. Both V(3)-O(10) bond lengths are 1.91 Å. Both V(3)-O(2) bond lengths are 1.99 Å. Co(1) is bonded in a square co-planar geometry to two equivalent O(4) and two equivalent O(8) atoms. Both Co(1)-O(4) bond lengths are 2.13 Å. Both Co(1)-O(8) bond lengths are 2.09 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra and  a cornercorner with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-48°. The P(1)-O(2) bond length is 1.52 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(1), one O(4), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra and  a cornercorner with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-47°. The P(2)-O(1) bond length is 1.53 Å. The P(2)-O(4) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.55 Å. The P(2)-O(9) bond length is 1.55 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(3) and one P(2) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one V(3) and one P(1) atom. In the third O site, O(3) is bonded in a distorted L-shaped geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Co(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted L-shaped geometry to one V(1) and one P(1) 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(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one V(1) and one Co(1) atom. In the ninth O site, O(9) is bonded in a 2-coordinate geometry to one V(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one V(2) and one V(3) atom. Linkers: 4 [O]P([O])([O])=O. Metal clusters: 4 [V] ,1 [Co]. The MOF has largest included sphere 4.34 A, density 1.66 g/cm3, surface area 2593.34 m2/g, accessible volume 0.33 cm3/g