VO2 is Pb(Zr_(1-x)Ti_x)O3-derived structured and crystallizes in the orthorhombic Pma2 space group. There are seven inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(6), one O(7), one O(9), and two equivalent O(4) atoms to form a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 6-26°. In the second V site, V(2) is bonded to one O(1), one O(11), one O(12), one O(4), one O(6), and one O(7) atom to form a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 2-26°. In the third V site, V(3) is bonded to two equivalent O(12), two equivalent O(2), 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 2-25°. In the fourth V site, V(4) is bonded to one O(3), one O(5), one O(8), one O(9), and two equivalent O(2) atoms to form a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(10), one O(13), one O(3), one O(5), and two equivalent O(2) atoms. In the sixth V site, V(6) is bonded to one O(13), one O(6), one O(7), one O(8), and two equivalent O(1) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-22°. In the seventh V site, V(7) is bonded in a 6-coordinate geometry to two equivalent O(11), two equivalent O(2), and two equivalent O(3) atoms. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to two equivalent V(2) and two equivalent V(6) atoms. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one V(3), one V(4), one V(5), and one V(7) atom. In the third O site, O(3) is bonded to one V(4), one V(5), and two equivalent V(7) atoms to form distorted corner-sharing OV4 tetrahedra. In the fourth O site, O(4) is bonded in a distorted see-saw-like geometry to two equivalent V(1) and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a distorted see-saw-like geometry to one V(4), one V(5), and two equivalent V(3) atoms. In the sixth O site, O(6) is bonded in a distorted see-saw-like geometry to one V(1), one V(6), and two equivalent V(2) atoms. In the seventh O site, O(7) is bonded in a distorted trigonal pyramidal geometry to one V(1), one V(6), and two equivalent V(2) atoms. In the eighth O site, O(8) is bonded in a linear geometry to one V(4) and one V(6) atom. In the ninth O site, O(9) is bonded in a linear geometry to one V(1) and one V(4) atom. In the tenth O site, O(10) is bonded in a linear geometry to one V(1) and one V(5) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one V(2) and one V(7) atom. In the twelfth O site, O(12) is bonded in a linear geometry to one V(2) and one V(3) atom. In the thirteenth O site, O(13) is bonded in a linear geometry to one V(5) and one V(6) atom.
VO2 is Pb(Zr_(1-x)Ti_x)O3-derived structured and crystallizes in the orthorhombic Pma2 space group. There are seven inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(6), one O(7), one O(9), and two equivalent O(4) atoms to form a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 6-26°. The V(1)-O(10) bond length is 1.95 Å. The V(1)-O(6) bond length is 2.09 Å. The V(1)-O(7) bond length is 2.22 Å. The V(1)-O(9) bond length is 1.70 Å. Both V(1)-O(4) bond lengths are 1.99 Å. In the second V site, V(2) is bonded to one O(1), one O(11), one O(12), one O(4), one O(6), and one O(7) atom to form a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 2-26°. The V(2)-O(1) bond length is 2.20 Å. The V(2)-O(11) bond length is 1.95 Å. The V(2)-O(12) bond length is 1.71 Å. The V(2)-O(4) bond length is 2.11 Å. The V(2)-O(6) bond length is 1.99 Å. The V(2)-O(7) bond length is 1.98 Å. In the third V site, V(3) is bonded to two equivalent O(12), two equivalent O(2), 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 2-25°. Both V(3)-O(12) bond lengths are 1.94 Å. Both V(3)-O(2) bond lengths are 2.13 Å. Both V(3)-O(5) bond lengths are 1.98 Å. In the fourth V site, V(4) is bonded to one O(3), one O(5), one O(8), one O(9), and two equivalent O(2) atoms to form a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. The V(4)-O(3) bond length is 2.09 Å. The V(4)-O(5) bond length is 2.12 Å. The V(4)-O(8) bond length is 1.72 Å. The V(4)-O(9) bond length is 1.95 Å. Both V(4)-O(2) bond lengths are 2.03 Å. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(10), one O(13), one O(3), one O(5), and two equivalent O(2) atoms. The V(5)-O(10) bond length is 1.71 Å. The V(5)-O(13) bond length is 1.68 Å. The V(5)-O(3) bond length is 2.30 Å. The V(5)-O(5) bond length is 2.24 Å. Both V(5)-O(2) bond lengths are 1.96 Å. In the sixth V site, V(6) is bonded to one O(13), one O(6), one O(7), one O(8), and two equivalent O(1) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-22°. The V(6)-O(13) bond length is 1.98 Å. The V(6)-O(6) bond length is 2.12 Å. The V(6)-O(7) bond length is 2.11 Å. The V(6)-O(8) bond length is 1.91 Å. Both V(6)-O(1) bond lengths are 1.97 Å. In the seventh V site, V(7) is bonded in a 6-coordinate geometry to two equivalent O(11), two equivalent O(2), and two equivalent O(3) atoms. Both V(7)-O(11) bond lengths are 1.70 Å. Both V(7)-O(2) bond lengths are 2.21 Å. Both V(7)-O(3) bond lengths are 2.00 Å. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to two equivalent V(2) and two equivalent V(6) atoms. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one V(3), one V(4), one V(5), and one V(7) atom. In the third O site, O(3) is bonded to one V(4), one V(5), and two equivalent V(7) atoms to form distorted corner-sharing OV4 tetrahedra. In the fourth O site, O(4) is bonded in a distorted see-saw-like geometry to two equivalent V(1) and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a distorted see-saw-like geometry to one V(4), one V(5), and two equivalent V(3) atoms. In the sixth O site, O(6) is bonded in a distorted see-saw-like geometry to one V(1), one V(6), and two equivalent V(2) atoms. In the seventh O site, O(7) is bonded in a distorted trigonal pyramidal geometry to one V(1), one V(6), and two equivalent V(2) atoms. In the eighth O site, O(8) is bonded in a linear geometry to one V(4) and one V(6) atom. In the ninth O site, O(9) is bonded in a linear geometry to one V(1) and one V(4) atom. In the tenth O site, O(10) is bonded in a linear geometry to one V(1) and one V(5) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one V(2) and one V(7) atom. In the twelfth O site, O(12) is bonded in a linear geometry to one V(2) and one V(3) atom. In the thirteenth O site, O(13) is bonded in a linear geometry to one V(5) and one V(6) atom.