Li2VO2F is Caswellsilverite-derived structured and crystallizes in the orthorhombic Pmm2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Li(3)O4F2 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent Li(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with four equivalent Li(1)O2F4 octahedra, and edges with four equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. In the third Li site, Li(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Li(1)O2F4 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. In the fourth Li site, Li(4) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(2) atoms to form LiO4F2 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one Li(2)O2F4 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with four equivalent Li(1)O2F4 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one Li(2)O2F4 octahedra,  an edgeedge with one Li(4)O4F2 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(3)O4F2 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Li(1)O2F4 octahedra,  an edgeedge with one Li(3)O4F2 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent Li(4)O4F2 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(4), and two equivalent V(2) atoms to form OLi4V2 octahedra that share corners with two equivalent O(3)Li2V4 octahedra, corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li6 octahedra,  an edgeedge with one O(3)Li2V4 octahedra,  an edgeedge with one F(1)Li6 octahedra, edges with two equivalent O(1)Li4V2 octahedra, edges with four equivalent O(4)Li2V4 octahedra, and edges with four equivalent F(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. In the second O site, O(2) is bonded to two equivalent Li(2), two equivalent Li(3), and two equivalent V(1) atoms to form OLi4V2 octahedra that share corners with two equivalent O(4)Li2V4 octahedra, corners with two equivalent O(2)Li4V2 octahedra, corners with two equivalent F(2)Li6 octahedra,  an edgeedge with one O(4)Li2V4 octahedra,  an edgeedge with one F(2)Li6 octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with four equivalent O(3)Li2V4 octahedra, and edges with four equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. In the third O site, O(3) is bonded to two equivalent Li(3), two equivalent V(1), and two equivalent V(2) atoms to form OLi2V4 octahedra that share corners with two equivalent O(3)Li2V4 octahedra, corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li6 octahedra,  an edgeedge with one O(1)Li4V2 octahedra,  an edgeedge with one F(1)Li6 octahedra, edges with two equivalent O(3)Li2V4 octahedra, edges with four equivalent O(4)Li2V4 octahedra, and edges with four equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. In the fourth O site, O(4) is bonded to two equivalent Li(4), two equivalent V(1), and two equivalent V(2) atoms to form OLi2V4 octahedra that share corners with two equivalent O(4)Li2V4 octahedra, corners with two equivalent O(2)Li4V2 octahedra, corners with two equivalent F(2)Li6 octahedra,  an edgeedge with one O(2)Li4V2 octahedra,  an edgeedge with one F(2)Li6 octahedra, edges with two equivalent O(4)Li2V4 octahedra, edges with four equivalent O(3)Li2V4 octahedra, and edges with four equivalent O(1)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. There are two inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form FLi6 octahedra that share corners with two equivalent O(3)Li2V4 octahedra, corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li6 octahedra,  an edgeedge with one O(3)Li2V4 octahedra,  an edgeedge with one O(1)Li4V2 octahedra, edges with two equivalent F(1)Li6 octahedra, edges with four equivalent O(2)Li4V2 octahedra, and edges with four equivalent F(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. In the second F site, F(2) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(4) atoms to form FLi6 octahedra that share corners with two equivalent O(4)Li2V4 octahedra, corners with two equivalent O(2)Li4V2 octahedra, corners with two equivalent F(2)Li6 octahedra,  an edgeedge with one O(4)Li2V4 octahedra,  an edgeedge with one O(2)Li4V2 octahedra, edges with two equivalent F(2)Li6 octahedra, edges with four equivalent O(1)Li4V2 octahedra, and edges with four equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°.
Li2VO2F is Caswellsilverite-derived structured and crystallizes in the orthorhombic Pmm2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Li(3)O4F2 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent Li(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. Both Li(1)-O(1) bond lengths are 2.14 Å. Both Li(1)-F(1) bond lengths are 2.06 Å. Both Li(1)-F(2) bond lengths are 2.11 Å. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with four equivalent Li(1)O2F4 octahedra, and edges with four equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. Both Li(2)-O(2) bond lengths are 2.15 Å. Both Li(2)-F(1) bond lengths are 2.11 Å. Both Li(2)-F(2) bond lengths are 2.06 Å. In the third Li site, Li(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Li(1)O2F4 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. Both Li(3)-O(2) bond lengths are 2.12 Å. Both Li(3)-O(3) bond lengths are 2.31 Å. Both Li(3)-F(1) bond lengths are 2.01 Å. In the fourth Li site, Li(4) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(2) atoms to form LiO4F2 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one Li(2)O2F4 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with four equivalent Li(1)O2F4 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. Both Li(4)-O(1) bond lengths are 2.12 Å. Both Li(4)-O(4) bond lengths are 2.30 Å. Both Li(4)-F(2) bond lengths are 2.01 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one Li(2)O2F4 octahedra,  an edgeedge with one Li(4)O4F2 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(3)O4F2 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. Both V(1)-O(2) bond lengths are 1.99 Å. Both V(1)-O(3) bond lengths are 2.12 Å. Both V(1)-O(4) bond lengths are 2.07 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Li(1)O2F4 octahedra,  an edgeedge with one Li(3)O4F2 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent Li(4)O4F2 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. Both V(2)-O(1) bond lengths are 1.99 Å. Both V(2)-O(3) bond lengths are 2.07 Å. Both V(2)-O(4) bond lengths are 2.12 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(4), and two equivalent V(2) atoms to form OLi4V2 octahedra that share corners with two equivalent O(3)Li2V4 octahedra, corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li6 octahedra,  an edgeedge with one O(3)Li2V4 octahedra,  an edgeedge with one F(1)Li6 octahedra, edges with two equivalent O(1)Li4V2 octahedra, edges with four equivalent O(4)Li2V4 octahedra, and edges with four equivalent F(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. In the second O site, O(2) is bonded to two equivalent Li(2), two equivalent Li(3), and two equivalent V(1) atoms to form OLi4V2 octahedra that share corners with two equivalent O(4)Li2V4 octahedra, corners with two equivalent O(2)Li4V2 octahedra, corners with two equivalent F(2)Li6 octahedra,  an edgeedge with one O(4)Li2V4 octahedra,  an edgeedge with one F(2)Li6 octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with four equivalent O(3)Li2V4 octahedra, and edges with four equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. In the third O site, O(3) is bonded to two equivalent Li(3), two equivalent V(1), and two equivalent V(2) atoms to form OLi2V4 octahedra that share corners with two equivalent O(3)Li2V4 octahedra, corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li6 octahedra,  an edgeedge with one O(1)Li4V2 octahedra,  an edgeedge with one F(1)Li6 octahedra, edges with two equivalent O(3)Li2V4 octahedra, edges with four equivalent O(4)Li2V4 octahedra, and edges with four equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. In the fourth O site, O(4) is bonded to two equivalent Li(4), two equivalent V(1), and two equivalent V(2) atoms to form OLi2V4 octahedra that share corners with two equivalent O(4)Li2V4 octahedra, corners with two equivalent O(2)Li4V2 octahedra, corners with two equivalent F(2)Li6 octahedra,  an edgeedge with one O(2)Li4V2 octahedra,  an edgeedge with one F(2)Li6 octahedra, edges with two equivalent O(4)Li2V4 octahedra, edges with four equivalent O(3)Li2V4 octahedra, and edges with four equivalent O(1)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. There are two inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form FLi6 octahedra that share corners with two equivalent O(3)Li2V4 octahedra, corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li6 octahedra,  an edgeedge with one O(3)Li2V4 octahedra,  an edgeedge with one O(1)Li4V2 octahedra, edges with two equivalent F(1)Li6 octahedra, edges with four equivalent O(2)Li4V2 octahedra, and edges with four equivalent F(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. In the second F site, F(2) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(4) atoms to form FLi6 octahedra that share corners with two equivalent O(4)Li2V4 octahedra, corners with two equivalent O(2)Li4V2 octahedra, corners with two equivalent F(2)Li6 octahedra,  an edgeedge with one O(4)Li2V4 octahedra,  an edgeedge with one O(2)Li4V2 octahedra, edges with two equivalent F(2)Li6 octahedra, edges with four equivalent O(1)Li4V2 octahedra, and edges with four equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°.