VO2 crystallizes in the monoclinic C2 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 16-26°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 16-23°. In the third V site, V(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 23°. In the fourth V site, V(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 23-26°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one V(1), one V(2), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one V(2), one V(3), and one V(4) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(4) atom. In the fourth O site, O(4) is bonded in a T-shaped geometry to one V(2), one V(3), and one V(4) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(4) atom. In the sixth O site, O(6) is bonded in a T-shaped geometry to one V(2), one V(3), and one V(4) atom.
VO2 crystallizes in the monoclinic C2 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 16-26°. Both V(1)-O(1) bond lengths are 2.02 Å. Both V(1)-O(3) bond lengths are 2.04 Å. Both V(1)-O(5) bond lengths are 2.06 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 16-23°. The V(2)-O(1) bond length is 1.99 Å. The V(2)-O(2) bond length is 1.86 Å. The V(2)-O(3) bond length is 1.78 Å. The V(2)-O(4) bond length is 1.94 Å. The V(2)-O(5) bond length is 1.99 Å. The V(2)-O(6) bond length is 1.91 Å. In the third V site, V(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 23°. Both V(3)-O(2) bond lengths are 2.06 Å. Both V(3)-O(4) bond lengths are 2.04 Å. Both V(3)-O(6) bond lengths are 2.00 Å. In the fourth V site, V(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 23-26°. The V(4)-O(1) bond length is 1.94 Å. The V(4)-O(2) bond length is 1.99 Å. The V(4)-O(3) bond length is 2.16 Å. The V(4)-O(4) bond length is 1.91 Å. The V(4)-O(5) bond length is 1.85 Å. The V(4)-O(6) bond length is 1.95 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one V(1), one V(2), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one V(2), one V(3), and one V(4) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(4) atom. In the fourth O site, O(4) is bonded in a T-shaped geometry to one V(2), one V(3), and one V(4) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(4) atom. In the sixth O site, O(6) is bonded in a T-shaped geometry to one V(2), one V(3), and one V(4) atom.