V3O8 crystallizes in the monoclinic C2/m space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), and three equivalent O(4) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one V(1) and one O(1) atom. In the second O site, O(2) is bonded in a linear geometry to one V(1) and one V(2) atom. In the third O site, O(3) is bonded in a single-bond geometry to one V(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to three equivalent V(2) atoms.
V3O8 crystallizes in the monoclinic C2/m space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both V(1)-O(1) bond lengths are 1.91 Å. Both V(1)-O(2) bond lengths are 1.83 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), and three equivalent O(4) atoms. The V(2)-O(2) bond length is 1.81 Å. The V(2)-O(3) bond length is 1.61 Å. There are two shorter (1.91 Å) and one longer (2.05 Å) V(2)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one V(1) and one O(1) atom. The O(1)-O(1) bond length is 1.38 Å. In the second O site, O(2) is bonded in a linear geometry to one V(1) and one V(2) atom. In the third O site, O(3) is bonded in a single-bond geometry to one V(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to three equivalent V(2) atoms.