V4NiC4H4(NO5)2 crystallizes in the orthorhombic Cmcm space group. V(1) is bonded to one O(1), one O(3), and three equivalent O(2) atoms to form distorted VO5 trigonal bipyramids that share  a cornercorner with one Ni(1)N2O4 octahedra, corners with three equivalent V(1)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 41°. The V(1)-O(1) bond length is 1.64 Å. The V(1)-O(3) bond length is 1.79 Å. There are two shorter (1.89 Å) and one longer (2.05 Å) V(1)-O(2) bond length. Ni(1) is bonded to one N(1), one N(2), and four equivalent O(1) atoms to form NiN2O4 octahedra that share corners with four equivalent V(1)O5 trigonal bipyramids. The Ni(1)-N(1) bond length is 2.03 Å. The Ni(1)-N(2) bond length is 2.01 Å. All Ni(1)-O(1) bond lengths are 2.04 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 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 1.34 Å. The C(1)-H(1) bond length is 1.09 Å. In the second C site, C(2) is bonded in a distorted trigonal planar geometry to one C(1), one N(2), and one H(2) atom. The C(2)-N(2) bond length is 1.34 Å. The C(2)-H(2) 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 Ni(1) and two equivalent C(1) atoms. In the second N site, N(2) is bonded in a trigonal planar geometry to one Ni(1) and two equivalent C(2) atoms. There are two 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. There are three inequivalent O sites. In the first O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to three equivalent V(1) atoms. In the second O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the third O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Ni(1) atom. Linkers: 2 c1cnccn1. Metal clusters: 8 [V] ,2 [Ni]. The MOF has largest included sphere 1.72 A, density 2.97 g/cm3, surface area 2042.92 m2/g, accessible volume 0.05 cm3/g