VH8(C2O)5 crystallizes in the orthorhombic Pnma space group. V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 51°. Both V(1)-O(1) bond lengths are 1.97 Å. Both V(1)-O(2) bond lengths are 1.96 Å. There is one shorter (1.62 Å) and one longer (2.14 Å) V(1)-O(3) bond length. There are five inequivalent C sites. In the first C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(3), and one C(5) atom. The C(2)-C(1) bond length is 1.42 Å. The C(2)-C(3) bond length is 1.38 Å. The C(2)-C(5) bond length is 1.52 Å. In the second C site, C(1) is bonded in a trigonal planar geometry to one C(2), one C(3), and one C(4) atom. The C(1)-C(3) bond length is 1.38 Å. The C(1)-C(4) bond length is 1.50 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(1), one C(2), and one H(1) atom. The C(3)-H(1) bond length is 0.93 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one C(1), one O(1), and one O(2) atom. The C(4)-O(1) bond length is 1.26 Å. The C(4)-O(2) bond length is 1.27 Å. In the fifth C site, C(5) is bonded in a trigonal non-coplanar geometry to one C(2) and three equivalent H(2,3,4) atoms. All C(5)-H(2,3,4) bond lengths are 0.96 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(3) atom. In the second H site, H(2,3,4) is bonded in a single-bond geometry to one C(5) atom. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one V(1) and one C(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one C(4) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to two equivalent V(1) atoms. Linkers: 4 Cc1cc(C([O])=O)c(C)cc1C([O])=O. Metal clusters: 4 [V]. RCSR code: lvt. The MOF has largest included sphere 6.53 A, density 1.16 g/cm3, surface area 3982.09 m2/g, accessible volume 0.42 cm3/g