VH6(C3O)6 crystallizes in the cubic P4_332 space group. V(1) is bonded in a distorted octahedral geometry to six equivalent O(1) atoms. All V(1)-O(1) bond lengths are 1.89 Å. There are three inequivalent C sites. In the first C site, C(1) is bonded in a single-bond geometry to one C(3) and one O(1) atom. The C(1)-C(3) bond length is 1.38 Å. The C(1)-O(1) bond length is 1.27 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one C(3) and two equivalent C(2) atoms. The C(2)-C(3) bond length is 1.39 Å. There is one shorter (1.46 Å) and one longer (1.47 Å) C(2)-C(2) bond length. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(1), one C(2), and one H(1) atom. The C(3)-H(1) bond length is 1.14 Å. H(1) is bonded in a single-bond geometry to one C(3) atom. O(1) is bonded in a bent 120 degrees geometry to one V(1) and one C(1) atom. Linkers: 4 O=C1[CH]c2c3c(c4c(c2[CH]C1=O)[CH]C(=O)C(=O)[CH]4)[CH]C(=O)C(=O)[CH]3. Metal clusters: 4 [C]1=[C]O[V]23(O1)(O[C]=[C]O2)O[C]=[C]O3. RCSR code: srs. The MOF has largest included sphere 11.39 A, density 0.44 g/cm3, surface area 3833.20 m2/g, accessible volume 1.81 cm3/g