V2CuC4H3(NO3)2 crystallizes in the orthorhombic Pnma space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form VO4 tetrahedra that share corners with two equivalent Cu(1)N2O4 octahedra,  a cornercorner with one V(1)O4 tetrahedra, and  a cornercorner with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-58°. The V(1)-O(2) bond length is 1.70 Å. The V(1)-O(4) bond length is 1.80 Å. The V(1)-O(5) bond length is 1.62 Å. The V(1)-O(6) bond length is 1.80 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), and one O(7) atom to form VO4 tetrahedra that share corners with two equivalent Cu(1)N2O4 octahedra,  a cornercorner with one V(1)O4 tetrahedra, and  a cornercorner with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-21°. The V(2)-O(1) bond length is 1.64 Å. The V(2)-O(3) bond length is 1.68 Å. The V(2)-O(4) bond length is 1.79 Å. The V(2)-O(7) bond length is 1.79 Å. Cu(1) is bonded to one N(1), one N(2), one O(1), one O(3), and two equivalent O(2) atoms to form distorted CuN2O4 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and  an edgeedge with one Cu(1)N2O4 octahedra. The Cu(1)-N(1) bond length is 2.06 Å. The Cu(1)-N(2) bond length is 2.03 Å. The Cu(1)-O(1) bond length is 2.32 Å. The Cu(1)-O(3) bond length is 1.91 Å. There is one shorter (1.92 Å) and one longer (2.62 Å) Cu(1)-O(2) bond length. There are six inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal planar geometry to one C(2), one N(1), and one H(1) atom. The C(1)-C(2) bond length is 1.39 Å. The C(1)-N(1) bond length is 1.35 Å. The C(1)-H(1) bond length is 1.09 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to two equivalent C(1) and one H(2) atom. The C(2)-H(2) bond length is 1.09 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(4) and two equivalent N(1) atoms. The C(3)-C(4) bond length is 1.46 Å. Both C(3)-N(1) bond lengths are 1.34 Å. In the fourth C site, C(4) is bonded in a distorted trigonal planar geometry to one C(3) and two equivalent N(2) atoms. Both C(4)-N(2) bond lengths are 1.33 Å. In the fifth C site, C(5) is bonded in a distorted trigonal planar geometry to one C(6), one N(2), and one H(3) atom. The C(5)-C(6) bond length is 1.39 Å. The C(5)-N(2) bond length is 1.34 Å. The C(5)-H(3) bond length is 1.09 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to two equivalent C(5) and one H(4) atom. The C(6)-H(4) bond length is 1.08 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Cu(1), one C(1), and one C(3) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Cu(1), one C(4), and one C(5) atom. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(5) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(6) atom. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a single-bond geometry to one V(1) atom. In the second O site, O(6) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the third O site, O(7) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. In the fourth O site, O(1) is bonded in a distorted linear geometry to one V(2) and one Cu(1) atom. In the fifth O site, O(2) is bonded in a distorted bent 150 degrees geometry to one V(1) and two equivalent Cu(1) atoms. In the sixth O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one Cu(1) atom. In the seventh O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. Linkers: 4 c1cnc(-c2ncccn2)nc1. Metal clusters: 16 [V] ,8 [Cu]. The MOF has largest included sphere 1.93 A, density 2.70 g/cm3, surface area 2275.10 m2/g, accessible volume 0.03 cm3/g