VO2 crystallizes in the triclinic P1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(11), one O(3), one O(5), one O(7), and one O(9) atom to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 19-24°. In the second V site, V(2) is bonded to one O(10), one O(12), one O(2), one O(4), one O(6), and one O(8) atom to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 17-23°. In the third V site, V(3) is bonded to one O(12), one O(2), one O(4), one O(6), one O(7), and one O(9) atom to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 19-24°. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(11), one O(3), one O(5), and one O(8) atom to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 17-23°. In the fifth V site, V(5) is bonded to one O(10), one O(11), one O(2), one O(4), one O(5), and one O(8) atom to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 19-24°. In the sixth V site, V(6) is bonded to one O(1), one O(12), one O(3), one O(6), one O(7), and one O(9) atom to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 17-23°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one V(1), one V(4), and one V(6) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one V(2), one V(3), and one V(5) atom. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one V(1), one V(4), and one V(6) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one V(2), one V(3), and one V(5) atom. In the fifth O site, O(5) is bonded in a T-shaped geometry to one V(1), one V(4), and one V(5) 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(6) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one V(1), one V(3), and one V(6) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one V(2), one V(4), and one V(5) atom. In the ninth O site, O(9) is bonded in a T-shaped geometry to one V(1), one V(3), and one V(6) atom. In the tenth O site, O(10) is bonded in a T-shaped geometry to one V(2), one V(4), and one V(5) atom. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one V(1), one V(4), and one V(5) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one V(6) atom.
VO2 crystallizes in the triclinic P1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(11), one O(3), one O(5), one O(7), and one O(9) atom to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 19-24°. The V(1)-O(1) bond length is 1.98 Å. The V(1)-O(11) bond length is 2.00 Å. The V(1)-O(3) bond length is 1.98 Å. The V(1)-O(5) bond length is 1.90 Å. The V(1)-O(7) bond length is 2.00 Å. The V(1)-O(9) bond length is 1.90 Å. In the second V site, V(2) is bonded to one O(10), one O(12), one O(2), one O(4), one O(6), and one O(8) atom to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 17-23°. The V(2)-O(10) bond length is 1.99 Å. The V(2)-O(12) bond length is 1.90 Å. The V(2)-O(2) bond length is 1.97 Å. The V(2)-O(4) bond length is 1.97 Å. The V(2)-O(6) bond length is 1.99 Å. The V(2)-O(8) bond length is 1.92 Å. In the third V site, V(3) is bonded to one O(12), one O(2), one O(4), one O(6), one O(7), and one O(9) atom to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 19-24°. The V(3)-O(12) bond length is 2.21 Å. The V(3)-O(2) bond length is 1.98 Å. The V(3)-O(4) bond length is 1.95 Å. The V(3)-O(6) bond length is 1.90 Å. The V(3)-O(7) bond length is 1.82 Å. The V(3)-O(9) bond length is 2.02 Å. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(11), one O(3), one O(5), and one O(8) atom to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 17-23°. The V(4)-O(1) bond length is 1.97 Å. The V(4)-O(10) bond length is 1.98 Å. The V(4)-O(11) bond length is 2.11 Å. The V(4)-O(3) bond length is 1.96 Å. The V(4)-O(5) bond length is 1.96 Å. The V(4)-O(8) bond length is 1.84 Å. In the fifth V site, V(5) is bonded to one O(10), one O(11), one O(2), one O(4), one O(5), and one O(8) atom to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 19-24°. The V(5)-O(10) bond length is 1.90 Å. The V(5)-O(11) bond length is 1.82 Å. The V(5)-O(2) bond length is 1.95 Å. The V(5)-O(4) bond length is 1.98 Å. The V(5)-O(5) bond length is 2.02 Å. The V(5)-O(8) bond length is 2.21 Å. In the sixth V site, V(6) is bonded to one O(1), one O(12), one O(3), one O(6), one O(7), and one O(9) atom to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 17-23°. The V(6)-O(1) bond length is 1.96 Å. The V(6)-O(12) bond length is 1.84 Å. The V(6)-O(3) bond length is 1.97 Å. The V(6)-O(6) bond length is 1.98 Å. The V(6)-O(7) bond length is 2.10 Å. The V(6)-O(9) bond length is 1.96 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one V(1), one V(4), and one V(6) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one V(2), one V(3), and one V(5) atom. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one V(1), one V(4), and one V(6) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one V(2), one V(3), and one V(5) atom. In the fifth O site, O(5) is bonded in a T-shaped geometry to one V(1), one V(4), and one V(5) 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(6) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one V(1), one V(3), and one V(6) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one V(2), one V(4), and one V(5) atom. In the ninth O site, O(9) is bonded in a T-shaped geometry to one V(1), one V(3), and one V(6) atom. In the tenth O site, O(10) is bonded in a T-shaped geometry to one V(2), one V(4), and one V(5) atom. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one V(1), one V(4), and one V(5) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one V(6) atom.