VO2 crystallizes in the triclinic P-1 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(5), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 17-26°. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 17-26°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one V(3) and two equivalent V(2) atoms. 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(3) atom.
VO2 crystallizes in the triclinic P-1 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(5), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 17-26°. The V(1)-O(1) bond length is 1.93 Å. The V(1)-O(5) bond length is 1.79 Å. There is one shorter (1.88 Å) and one longer (1.97 Å) V(1)-O(2) bond length. There is one shorter (1.96 Å) and one longer (2.03 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(2), one O(3), one O(5), and two equivalent O(4) atoms. The V(2)-O(1) bond length is 1.86 Å. The V(2)-O(2) bond length is 1.92 Å. The V(2)-O(3) bond length is 1.81 Å. The V(2)-O(5) bond length is 2.21 Å. There is one shorter (1.89 Å) and one longer (1.98 Å) V(2)-O(4) bond length. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 17-26°. Both V(3)-O(1) bond lengths are 1.97 Å. Both V(3)-O(4) bond lengths are 1.94 Å. Both V(3)-O(5) bond lengths are 1.88 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one V(3) and two equivalent V(2) atoms. 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(3) atom.