VO2 is Hydrophilite-like structured and crystallizes in the orthorhombic Pmn2_1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(5), one O(8), two equivalent O(2), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. In the second V site, V(2) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 49-53°. In the third V site, V(3) is bonded to one O(6), one O(7), two equivalent O(1), and two equivalent O(8) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-53°. In the fourth V site, V(4) is bonded to one O(2), one O(3), two equivalent O(4), and two equivalent O(6) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. There are eight 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(3) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(4) 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(4) and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(4) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(2) atoms. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one V(3) and two equivalent V(4) atoms. In the seventh O site, O(7) is bonded in a trigonal non-coplanar geometry to one V(3) and two equivalent V(1) atoms. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one V(1) and two equivalent V(3) atoms.
VO2 is Hydrophilite-like structured and crystallizes in the orthorhombic Pmn2_1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(5), one O(8), two equivalent O(2), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. The V(1)-O(5) bond length is 1.87 Å. The V(1)-O(8) bond length is 1.99 Å. Both V(1)-O(2) bond lengths are 2.00 Å. Both V(1)-O(7) bond lengths are 1.97 Å. In the second V site, V(2) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 49-53°. The V(2)-O(1) bond length is 1.94 Å. The V(2)-O(4) bond length is 1.85 Å. Both V(2)-O(3) bond lengths are 2.00 Å. Both V(2)-O(5) bond lengths are 2.00 Å. In the third V site, V(3) is bonded to one O(6), one O(7), two equivalent O(1), and two equivalent O(8) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-53°. The V(3)-O(6) bond length is 1.96 Å. The V(3)-O(7) bond length is 1.94 Å. Both V(3)-O(1) bond lengths are 2.02 Å. Both V(3)-O(8) bond lengths are 1.96 Å. In the fourth V site, V(4) is bonded to one O(2), one O(3), two equivalent O(4), and two equivalent O(6) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. The V(4)-O(2) bond length is 1.91 Å. The V(4)-O(3) bond length is 1.90 Å. Both V(4)-O(4) bond lengths are 2.03 Å. Both V(4)-O(6) bond lengths are 1.96 Å. There are eight 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(3) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(4) 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(4) and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(4) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(2) atoms. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one V(3) and two equivalent V(4) atoms. In the seventh O site, O(7) is bonded in a trigonal non-coplanar geometry to one V(3) and two equivalent V(1) atoms. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one V(1) and two equivalent V(3) atoms.