Li3V2(O2F)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one F(1), one F(2), and one F(3) atom. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), one F(3), and two equivalent F(2) atoms to form distorted LiO3F3 octahedra that share corners with three equivalent Li(2)O3F3 octahedra, corners with three equivalent V(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-20°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), and four equivalent O(2) atoms to form VO6 octahedra that share corners with three equivalent Li(2)O3F3 octahedra,  an edgeedge with one Li(2)O3F3 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-20°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one V(1), and two equivalent V(2) atoms to form OLi2V3 square pyramids that share corners with three equivalent O(3)Li3V3 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and  an edgeedge with one O(1)Li2V3 square pyramid. The corner-sharing octahedral tilt angles range from 3-5°. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(2), one V(2), and two equivalent V(1) atoms. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share corners with three equivalent F(3)Li6 octahedra, corners with three equivalent O(1)Li2V3 square pyramids,  an edgeedge with one O(3)Li3V3 octahedra, and edges with two equivalent O(1)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 13-20°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a square co-planar geometry to four equivalent Li(1) atoms. In the second F site, F(2) is bonded in a square co-planar geometry to two equivalent Li(1) and two equivalent Li(2) atoms. In the third F site, F(3) is bonded to two equivalent Li(2) and four equivalent Li(1) atoms to form distorted FLi6 octahedra that share corners with six equivalent O(3)Li3V3 octahedra and edges with two equivalent O(1)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 13-20°.
Li3V2(O2F)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one F(1), one F(2), and one F(3) atom. The Li(1)-O(1) bond length is 2.41 Å. The Li(1)-O(3) bond length is 2.25 Å. The Li(1)-F(1) bond length is 1.93 Å. The Li(1)-F(2) bond length is 1.87 Å. The Li(1)-F(3) bond length is 2.04 Å. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), one F(3), and two equivalent F(2) atoms to form distorted LiO3F3 octahedra that share corners with three equivalent Li(2)O3F3 octahedra, corners with three equivalent V(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-20°. The Li(2)-O(3) bond length is 2.23 Å. Both Li(2)-O(2) bond lengths are 2.29 Å. The Li(2)-F(3) bond length is 2.13 Å. Both Li(2)-F(2) bond lengths are 1.94 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), and four equivalent O(2) atoms to form VO6 octahedra that share corners with three equivalent Li(2)O3F3 octahedra,  an edgeedge with one Li(2)O3F3 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-20°. The V(1)-O(1) bond length is 2.06 Å. The V(1)-O(3) bond length is 2.05 Å. There are two shorter (2.02 Å) and two longer (2.04 Å) V(1)-O(2) bond lengths. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. Both V(2)-O(1) bond lengths are 1.98 Å. Both V(2)-O(2) bond lengths are 1.91 Å. Both V(2)-O(3) bond lengths are 2.06 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one V(1), and two equivalent V(2) atoms to form OLi2V3 square pyramids that share corners with three equivalent O(3)Li3V3 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and  an edgeedge with one O(1)Li2V3 square pyramid. The corner-sharing octahedral tilt angles range from 3-5°. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(2), one V(2), and two equivalent V(1) atoms. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share corners with three equivalent F(3)Li6 octahedra, corners with three equivalent O(1)Li2V3 square pyramids,  an edgeedge with one O(3)Li3V3 octahedra, and edges with two equivalent O(1)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 13-20°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a square co-planar geometry to four equivalent Li(1) atoms. In the second F site, F(2) is bonded in a square co-planar geometry to two equivalent Li(1) and two equivalent Li(2) atoms. In the third F site, F(3) is bonded to two equivalent Li(2) and four equivalent Li(1) atoms to form distorted FLi6 octahedra that share corners with six equivalent O(3)Li3V3 octahedra and edges with two equivalent O(1)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 13-20°.