V2O3 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedra are not tilted. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent V(2) and four equivalent V(1) atoms to form OV6 octahedra that share corners with four equivalent O(3)V5 square pyramids, edges with two equivalent O(1)V6 octahedra, and edges with six equivalent O(3)V5 square pyramids. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one V(1) and two equivalent V(2) atoms. In the third O site, O(3) is bonded to two equivalent V(2) and three equivalent V(1) atoms to form OV5 square pyramids that share corners with two equivalent O(1)V6 octahedra, edges with three equivalent O(1)V6 octahedra, and edges with four equivalent O(3)V5 square pyramids. The corner-sharing octahedral tilt angles are 9°. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms.
V2O3 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedra are not tilted. The V(1)-O(2) bond length is 1.89 Å. Both V(1)-O(1) bond lengths are 2.17 Å. There are two shorter (2.11 Å) and one longer (2.15 Å) V(1)-O(3) bond length. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms. The V(2)-O(1) bond length is 2.46 Å. The V(2)-O(4) bond length is 1.80 Å. Both V(2)-O(2) bond lengths are 1.97 Å. Both V(2)-O(3) bond lengths are 2.24 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent V(2) and four equivalent V(1) atoms to form OV6 octahedra that share corners with four equivalent O(3)V5 square pyramids, edges with two equivalent O(1)V6 octahedra, and edges with six equivalent O(3)V5 square pyramids. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one V(1) and two equivalent V(2) atoms. In the third O site, O(3) is bonded to two equivalent V(2) and three equivalent V(1) atoms to form OV5 square pyramids that share corners with two equivalent O(1)V6 octahedra, edges with three equivalent O(1)V6 octahedra, and edges with four equivalent O(3)V5 square pyramids. The corner-sharing octahedral tilt angles are 9°. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms.