VC8O5 crystallizes in the orthorhombic Imma space group. V(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 46°. Both V(1)-O(2) bond lengths are 1.85 Å. All V(1)-O(1) bond lengths are 1.94 Å. There are three inequivalent C sites. In the first C site, C(1) is bonded in a water-like geometry to one C(1) and one C(2) atom. The C(1)-C(1) bond length is 1.39 Å. The C(1)-C(2) bond length is 1.41 Å. In the second C site, C(2) is bonded in a distorted trigonal planar geometry to one C(3) and two equivalent C(1) atoms. The C(2)-C(3) bond length is 1.50 Å. In the third C site, C(3) is bonded in a water-like geometry to one C(2) and two equivalent O(1) atoms. Both C(3)-O(1) bond lengths are 1.35 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one C(3) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to two equivalent V(1) atoms. Linkers: 4 [O]C(=O)c1[c][c]c(C([O])=O)[c][c]1. Metal clusters: 4 [V]. The MOF has largest included sphere 7.06 A, density 1.03 g/cm3, surface area 3634.85 m2/g, accessible volume 0.53 cm3/g