VO2 crystallizes in the trigonal R3m space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2) and three equivalent O(1) atoms to form corner-sharing VO4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-59°. In the second V site, V(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra and edges with four equivalent V(2)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(2) atoms. In the second O site, O(2) is bonded in a distorted trigonal pyramidal geometry to one V(1) and three equivalent V(2) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to three equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a water-like geometry to two equivalent V(2) atoms.
VO2 crystallizes in the trigonal R3m space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2) and three equivalent O(1) atoms to form corner-sharing VO4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-59°. The V(1)-O(2) bond length is 1.94 Å. All V(1)-O(1) bond lengths are 1.82 Å. In the second V site, V(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra and edges with four equivalent V(2)O6 octahedra. The V(2)-O(2) bond length is 2.11 Å. The V(2)-O(3) bond length is 1.95 Å. Both V(2)-O(1) bond lengths are 2.09 Å. Both V(2)-O(4) bond lengths are 1.84 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(2) atoms. In the second O site, O(2) is bonded in a distorted trigonal pyramidal geometry to one V(1) and three equivalent V(2) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to three equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a water-like geometry to two equivalent V(2) atoms.