VO2 crystallizes in the monoclinic C2/c space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent V(2)O4 tetrahedra and edges with two equivalent V(1)O6 octahedra. In the second V site, V(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted corner-sharing VO4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-55°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a 2-coordinate geometry to one V(1) and one V(2) atom.
VO2 crystallizes in the monoclinic C2/c space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent V(2)O4 tetrahedra and edges with two equivalent V(1)O6 octahedra. Both V(1)-O(2) bond lengths are 2.03 Å. There are two shorter (2.05 Å) and two longer (2.09 Å) V(1)-O(1) bond lengths. In the second V site, V(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted corner-sharing VO4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-55°. Both V(2)-O(1) bond lengths are 1.83 Å. Both V(2)-O(2) bond lengths are 1.71 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a 2-coordinate geometry to one V(1) and one V(2) atom.