Li2VO2F is alpha Po-derived structured and crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with three equivalent Li(2)O3F3 octahedra, corners with three equivalent Li(1)O4F2 octahedra, edges with three equivalent Li(2)O3F3 octahedra, edges with three equivalent Li(1)O4F2 octahedra, and edges with six equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the second Li site, Li(2) is bonded to three equivalent O(3) and three equivalent F(1) atoms to form LiO3F3 octahedra that share corners with three equivalent Li(1)O4F2 octahedra, corners with three equivalent V(1)O5F octahedra, edges with three equivalent Li(1)O4F2 octahedra, edges with three equivalent V(1)O5F octahedra, and edges with six equivalent Li(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. V(1) is bonded to one O(2), two equivalent O(1), two equivalent O(3), and one F(1) atom to form VO5F octahedra that share corners with three equivalent Li(2)O3F3 octahedra, corners with three equivalent V(1)O5F octahedra, edges with three equivalent Li(2)O3F3 octahedra, edges with three equivalent V(1)O5F octahedra, and edges with six equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1) and four equivalent V(1) atoms to form OLi2V4 octahedra that share corners with six equivalent O(3)Li4V2 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with two equivalent O(3)Li4V2 octahedra, edges with four equivalent O(2)Li4V2 octahedra, and edges with four equivalent F(1)Li5V octahedra. The corner-sharing octahedral tilt angles range from 4-8°. In the second O site, O(2) is bonded to four equivalent Li(1) and two equivalent V(1) atoms to form OLi4V2 octahedra that share corners with six equivalent F(1)Li5V octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with two equivalent F(1)Li5V octahedra, edges with four equivalent O(1)Li2V4 octahedra, and edges with four equivalent O(3)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. In the third O site, O(3) is bonded to one Li(1), three equivalent Li(2), and two equivalent V(1) atoms to form OLi4V2 octahedra that share corners with three equivalent O(1)Li2V4 octahedra, corners with three equivalent F(1)Li5V octahedra,  an edgeedge with one O(1)Li2V4 octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with four equivalent O(3)Li4V2 octahedra, and edges with five equivalent F(1)Li5V octahedra. The corner-sharing octahedral tilt angles range from 2-10°. F(1) is bonded to two equivalent Li(1), three equivalent Li(2), and one V(1) atom to form FLi5V octahedra that share corners with three equivalent O(2)Li4V2 octahedra, corners with three equivalent O(3)Li4V2 octahedra,  an edgeedge with one O(2)Li4V2 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with four equivalent F(1)Li5V octahedra, and edges with five equivalent O(3)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°.
Li2VO2F is alpha Po-derived structured and crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with three equivalent Li(2)O3F3 octahedra, corners with three equivalent Li(1)O4F2 octahedra, edges with three equivalent Li(2)O3F3 octahedra, edges with three equivalent Li(1)O4F2 octahedra, and edges with six equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-10°. The Li(1)-O(1) bond length is 2.13 Å. The Li(1)-O(3) bond length is 2.01 Å. There is one shorter (2.11 Å) and one longer (2.12 Å) Li(1)-O(2) bond length. There is one shorter (2.11 Å) and one longer (2.12 Å) Li(1)-F(1) bond length. In the second Li site, Li(2) is bonded to three equivalent O(3) and three equivalent F(1) atoms to form LiO3F3 octahedra that share corners with three equivalent Li(1)O4F2 octahedra, corners with three equivalent V(1)O5F octahedra, edges with three equivalent Li(1)O4F2 octahedra, edges with three equivalent V(1)O5F octahedra, and edges with six equivalent Li(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. There are a spread of Li(2)-O(3) bond distances ranging from 2.05-2.12 Å. There is one shorter (2.17 Å) and two longer (2.18 Å) Li(2)-F(1) bond lengths. V(1) is bonded to one O(2), two equivalent O(1), two equivalent O(3), and one F(1) atom to form VO5F octahedra that share corners with three equivalent Li(2)O3F3 octahedra, corners with three equivalent V(1)O5F octahedra, edges with three equivalent Li(2)O3F3 octahedra, edges with three equivalent V(1)O5F octahedra, and edges with six equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. The V(1)-O(2) bond length is 1.94 Å. There is one shorter (2.09 Å) and one longer (2.17 Å) V(1)-O(1) bond length. There is one shorter (1.96 Å) and one longer (2.07 Å) V(1)-O(3) bond length. The V(1)-F(1) bond length is 2.14 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1) and four equivalent V(1) atoms to form OLi2V4 octahedra that share corners with six equivalent O(3)Li4V2 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with two equivalent O(3)Li4V2 octahedra, edges with four equivalent O(2)Li4V2 octahedra, and edges with four equivalent F(1)Li5V octahedra. The corner-sharing octahedral tilt angles range from 4-8°. In the second O site, O(2) is bonded to four equivalent Li(1) and two equivalent V(1) atoms to form OLi4V2 octahedra that share corners with six equivalent F(1)Li5V octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with two equivalent F(1)Li5V octahedra, edges with four equivalent O(1)Li2V4 octahedra, and edges with four equivalent O(3)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. In the third O site, O(3) is bonded to one Li(1), three equivalent Li(2), and two equivalent V(1) atoms to form OLi4V2 octahedra that share corners with three equivalent O(1)Li2V4 octahedra, corners with three equivalent F(1)Li5V octahedra,  an edgeedge with one O(1)Li2V4 octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with four equivalent O(3)Li4V2 octahedra, and edges with five equivalent F(1)Li5V octahedra. The corner-sharing octahedral tilt angles range from 2-10°. F(1) is bonded to two equivalent Li(1), three equivalent Li(2), and one V(1) atom to form FLi5V octahedra that share corners with three equivalent O(2)Li4V2 octahedra, corners with three equivalent O(3)Li4V2 octahedra,  an edgeedge with one O(2)Li4V2 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with four equivalent F(1)Li5V octahedra, and edges with five equivalent O(3)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°.