Li2VO2F is alpha Po-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), two equivalent O(1), one F(1), and one F(2) atom to form LiO4F2 octahedra that share corners with two equivalent Li(3)O3F3 octahedra, corners with two equivalent Li(4)O3F3 octahedra, corners with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(4)O3F3 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with three equivalent V(1)O5F octahedra, and edges with three equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the second Li site, Li(2) is bonded to one O(3), one O(4), two equivalent O(2), one F(1), and one F(2) atom to form LiO4F2 octahedra that share corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent V(1)O5F octahedra, corners with two equivalent V(2)O5F octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, edges with two equivalent V(2)O5F octahedra, edges with three equivalent Li(3)O3F3 octahedra, and edges with three equivalent Li(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one F(2), and two equivalent F(1) atoms to form LiO3F3 octahedra that share corners with two equivalent Li(3)O3F3 octahedra, corners with two equivalent Li(4)O3F3 octahedra, corners with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, edges with three equivalent Li(2)O4F2 octahedra, and edges with three equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(4), one F(1), and two equivalent F(2) atoms to form LiO3F3 octahedra that share corners with two equivalent Li(3)O3F3 octahedra, corners with two equivalent Li(4)O3F3 octahedra, corners with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, edges with three equivalent Li(2)O4F2 octahedra, and edges with three equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-6°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), two equivalent O(4), and one F(2) atom to form VO5F octahedra that share corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent V(1)O5F octahedra, corners with two equivalent V(2)O5F octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, edges with three equivalent Li(4)O3F3 octahedra, and edges with three equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-12°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), two equivalent O(3), and one F(1) atom to form VO5F octahedra that share corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent V(1)O5F octahedra, corners with two equivalent V(2)O5F octahedra, edges with two equivalent Li(4)O3F3 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, edges with three equivalent Li(3)O3F3 octahedra, and edges with three equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Li(4), two equivalent Li(1), one V(1), and one V(2) atom to form OLi4V2 octahedra that share corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li5V octahedra, corners with two equivalent F(2)Li5V octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with two equivalent F(1)Li5V octahedra, edges with two equivalent F(2)Li5V octahedra, edges with three equivalent O(3)Li3V3 octahedra, and edges with three equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. In the second O site, O(2) is bonded to one Li(3), one Li(4), two equivalent Li(2), one V(1), and one V(2) atom to form OLi4V2 octahedra that share corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(4)Li3V3 octahedra, corners with two equivalent O(2)Li4V2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(1)Li4V2 octahedra, edges with three equivalent F(1)Li5V octahedra, and edges with three equivalent F(2)Li5V octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(4)Li3V3 octahedra, corners with two equivalent O(2)Li4V2 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with two equivalent F(2)Li5V octahedra, edges with three equivalent O(1)Li4V2 octahedra, and edges with three equivalent F(1)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(4), one V(2), and two equivalent V(1) atoms to form OLi3V3 octahedra that share corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(4)Li3V3 octahedra, corners with two equivalent O(2)Li4V2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with two equivalent F(1)Li5V octahedra, edges with three equivalent O(1)Li4V2 octahedra, and edges with three equivalent F(2)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-12°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(4), two equivalent Li(3), and one V(2) atom to form FLi5V octahedra that share corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li5V octahedra, corners with two equivalent F(2)Li5V octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(1)Li4V2 octahedra, edges with two equivalent F(2)Li5V octahedra, edges with three equivalent O(3)Li3V3 octahedra, and edges with three equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), two equivalent Li(4), and one V(1) atom to form FLi5V octahedra that share corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li5V octahedra, corners with two equivalent F(2)Li5V octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(1)Li4V2 octahedra, edges with two equivalent F(1)Li5V octahedra, edges with three equivalent O(4)Li3V3 octahedra, and edges with three equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°.
Li2VO2F is alpha Po-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), two equivalent O(1), one F(1), and one F(2) atom to form LiO4F2 octahedra that share corners with two equivalent Li(3)O3F3 octahedra, corners with two equivalent Li(4)O3F3 octahedra, corners with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(4)O3F3 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with three equivalent V(1)O5F octahedra, and edges with three equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-6°. The Li(1)-O(3) bond length is 2.11 Å. The Li(1)-O(4) bond length is 2.10 Å. Both Li(1)-O(1) bond lengths are 2.08 Å. The Li(1)-F(1) bond length is 2.11 Å. The Li(1)-F(2) bond length is 2.12 Å. In the second Li site, Li(2) is bonded to one O(3), one O(4), two equivalent O(2), one F(1), and one F(2) atom to form LiO4F2 octahedra that share corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent V(1)O5F octahedra, corners with two equivalent V(2)O5F octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, edges with two equivalent V(2)O5F octahedra, edges with three equivalent Li(3)O3F3 octahedra, and edges with three equivalent Li(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. The Li(2)-O(3) bond length is 2.15 Å. The Li(2)-O(4) bond length is 2.11 Å. Both Li(2)-O(2) bond lengths are 2.08 Å. The Li(2)-F(1) bond length is 2.21 Å. The Li(2)-F(2) bond length is 2.24 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one F(2), and two equivalent F(1) atoms to form LiO3F3 octahedra that share corners with two equivalent Li(3)O3F3 octahedra, corners with two equivalent Li(4)O3F3 octahedra, corners with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, edges with three equivalent Li(2)O4F2 octahedra, and edges with three equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-7°. The Li(3)-O(1) bond length is 2.04 Å. The Li(3)-O(2) bond length is 2.10 Å. The Li(3)-O(3) bond length is 2.16 Å. The Li(3)-F(2) bond length is 2.01 Å. Both Li(3)-F(1) bond lengths are 2.08 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(4), one F(1), and two equivalent F(2) atoms to form LiO3F3 octahedra that share corners with two equivalent Li(3)O3F3 octahedra, corners with two equivalent Li(4)O3F3 octahedra, corners with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, edges with three equivalent Li(2)O4F2 octahedra, and edges with three equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-6°. The Li(4)-O(1) bond length is 2.05 Å. The Li(4)-O(2) bond length is 2.14 Å. The Li(4)-O(4) bond length is 2.10 Å. The Li(4)-F(1) bond length is 2.01 Å. Both Li(4)-F(2) bond lengths are 2.08 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), two equivalent O(4), and one F(2) atom to form VO5F octahedra that share corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent V(1)O5F octahedra, corners with two equivalent V(2)O5F octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, edges with three equivalent Li(4)O3F3 octahedra, and edges with three equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-12°. The V(1)-O(1) bond length is 1.94 Å. The V(1)-O(2) bond length is 1.99 Å. The V(1)-O(3) bond length is 2.07 Å. Both V(1)-O(4) bond lengths are 2.09 Å. The V(1)-F(2) bond length is 2.16 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), two equivalent O(3), and one F(1) atom to form VO5F octahedra that share corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent V(1)O5F octahedra, corners with two equivalent V(2)O5F octahedra, edges with two equivalent Li(4)O3F3 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, edges with three equivalent Li(3)O3F3 octahedra, and edges with three equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. The V(2)-O(1) bond length is 2.04 Å. The V(2)-O(2) bond length is 2.00 Å. The V(2)-O(4) bond length is 2.04 Å. Both V(2)-O(3) bond lengths are 2.08 Å. The V(2)-F(1) bond length is 2.13 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Li(4), two equivalent Li(1), one V(1), and one V(2) atom to form OLi4V2 octahedra that share corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li5V octahedra, corners with two equivalent F(2)Li5V octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with two equivalent F(1)Li5V octahedra, edges with two equivalent F(2)Li5V octahedra, edges with three equivalent O(3)Li3V3 octahedra, and edges with three equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. In the second O site, O(2) is bonded to one Li(3), one Li(4), two equivalent Li(2), one V(1), and one V(2) atom to form OLi4V2 octahedra that share corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(4)Li3V3 octahedra, corners with two equivalent O(2)Li4V2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(1)Li4V2 octahedra, edges with three equivalent F(1)Li5V octahedra, and edges with three equivalent F(2)Li5V octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(4)Li3V3 octahedra, corners with two equivalent O(2)Li4V2 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with two equivalent F(2)Li5V octahedra, edges with three equivalent O(1)Li4V2 octahedra, and edges with three equivalent F(1)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(4), one V(2), and two equivalent V(1) atoms to form OLi3V3 octahedra that share corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(4)Li3V3 octahedra, corners with two equivalent O(2)Li4V2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with two equivalent F(1)Li5V octahedra, edges with three equivalent O(1)Li4V2 octahedra, and edges with three equivalent F(2)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-12°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(4), two equivalent Li(3), and one V(2) atom to form FLi5V octahedra that share corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li5V octahedra, corners with two equivalent F(2)Li5V octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(1)Li4V2 octahedra, edges with two equivalent F(2)Li5V octahedra, edges with three equivalent O(3)Li3V3 octahedra, and edges with three equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), two equivalent Li(4), and one V(1) atom to form FLi5V octahedra that share corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li5V octahedra, corners with two equivalent F(2)Li5V octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(1)Li4V2 octahedra, edges with two equivalent F(1)Li5V octahedra, edges with three equivalent O(4)Li3V3 octahedra, and edges with three equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°.