V2CoC4H4(NO3)2 crystallizes in the orthorhombic Pnna space group. V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form VO4 tetrahedra that share corners with two equivalent Co(1)N2O4 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-44°. The V(1)-O(1) bond length is 1.68 Å. The V(1)-O(2) bond length is 1.79 Å. The V(1)-O(3) bond length is 1.78 Å. The V(1)-O(4) bond length is 1.67 Å. Co(1) is bonded to two equivalent N(1), two equivalent O(1), and two equivalent O(4) atoms to form CoN2O4 octahedra that share corners with four equivalent V(1)O4 tetrahedra. Both Co(1)-N(1) bond lengths are 2.00 Å. Both Co(1)-O(1) bond lengths are 1.95 Å. Both Co(1)-O(4) bond lengths are 1.97 Å. There are two inequivalent C sites. In the first C site, C(2) is bonded in a distorted bent 120 degrees geometry to one N(1) and one H(1) atom. The C(2)-N(1) bond length is 1.35 Å. The C(2)-H(1) bond length is 1.08 Å. In the second C site, C(1) is bonded in a distorted bent 120 degrees geometry to one N(1) and one H(2) atom. The C(1)-N(1) bond length is 1.35 Å. The C(1)-H(2) bond length is 1.09 Å. N(1) is bonded in a trigonal planar geometry to one Co(1), one C(1), and one C(2) atom. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(1) atom. There are four inequivalent O sites. In the first O site, O(3) is bonded in a bent 120 degrees geometry to two equivalent V(1) atoms. In the second O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one Co(1) atom. In the third O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the fourth O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Co(1) atom. Linkers: 4 c1cnccn1. Metal clusters: 8 [V] ,4 [Co]. The MOF has largest included sphere 1.64 A, density 2.68 g/cm3, surface area 2190.97 m2/g, accessible volume 0.06 cm3/g