Li3V2(O2F)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form distorted LiO3F3 octahedra that share corners with two equivalent Li(1)O3F3 octahedra, corners with three equivalent V(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with three equivalent Li(2)O3F3 octahedra, and edges with three equivalent Li(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 0-17°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one F(1), and two equivalent F(3) atoms to form distorted LiO3F3 octahedra that share  a cornercorner with one Li(2)O3F3 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(3)O3F3 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with three equivalent Li(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 0-17°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(4), one F(2), and two equivalent F(3) atoms to form distorted LiO3F3 octahedra that share  a cornercorner with one Li(3)O3F3 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Li(2)O3F3 octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with three equivalent Li(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 0-16°. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O3F3 octahedra, corners with four equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-16°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent Li(3)O3F3 octahedra, corners with four equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-17°. In the third V site, V(3) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O3F3 octahedra,  an edgeedge with one Li(1)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-17°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one O(3)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid, corners with two equivalent O(1)Li2V3 square pyramids, corners with two equivalent F(3)Li5 trigonal bipyramids, edges with three equivalent O(2)Li3V3 octahedra, edges with two equivalent O(3)Li2V3 square pyramids, edges with two equivalent O(4)Li2V3 square pyramids, and  an edgeedge with one F(3)Li5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 5°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with two equivalent O(2)Li3V3 octahedra,  a cornercorner with one O(1)Li2V3 square pyramid, corners with three equivalent F(3)Li5 trigonal bipyramids, edges with three equivalent O(1)Li2V3 square pyramids, edges with three equivalent O(3)Li2V3 square pyramids, edges with three equivalent O(4)Li2V3 square pyramids, and  an edgeedge with one F(3)Li5 trigonal bipyramid. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Li(1), one Li(2), one V(1), and two equivalent V(3) atoms to form distorted OLi2V3 square pyramids that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(3)Li2V3 square pyramid, corners with three equivalent O(4)Li2V3 square pyramids,  a cornercorner with one F(3)Li5 trigonal bipyramid, edges with three equivalent O(2)Li3V3 octahedra,  an edgeedge with one O(3)Li2V3 square pyramid,  an edgeedge with one O(4)Li2V3 square pyramid, edges with two equivalent O(1)Li2V3 square pyramids, and  an edgeedge with one F(3)Li5 trigonal bipyramid. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(2), and two equivalent V(3) atoms to form distorted OLi2V3 square pyramids that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid, corners with three equivalent O(3)Li2V3 square pyramids,  a cornercorner with one F(3)Li5 trigonal bipyramid, edges with three equivalent O(2)Li3V3 octahedra,  an edgeedge with one O(3)Li2V3 square pyramid,  an edgeedge with one O(4)Li2V3 square pyramid, edges with two equivalent O(1)Li2V3 square pyramids, and  an edgeedge with one F(3)Li5 trigonal bipyramid. There are three inequivalent F sites. In the first F site, F(1) is bonded in a square co-planar geometry to two equivalent Li(1) and two equivalent Li(2) 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(3) atoms. In the third F site, F(3) is bonded to one Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form FLi5 trigonal bipyramids that share corners with three equivalent O(2)Li3V3 octahedra,  a cornercorner with one O(3)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid, corners with two equivalent O(1)Li2V3 square pyramids,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(3)Li2V3 square pyramid,  an edgeedge with one O(4)Li2V3 square pyramid, and edges with two equivalent F(3)Li5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 12-18°.
Li3V2(O2F)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form distorted LiO3F3 octahedra that share corners with two equivalent Li(1)O3F3 octahedra, corners with three equivalent V(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with three equivalent Li(2)O3F3 octahedra, and edges with three equivalent Li(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 0-17°. The Li(1)-O(2) bond length is 2.33 Å. The Li(1)-O(3) bond length is 2.43 Å. The Li(1)-O(4) bond length is 2.43 Å. The Li(1)-F(1) bond length is 1.90 Å. The Li(1)-F(2) bond length is 1.89 Å. The Li(1)-F(3) bond length is 1.94 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one F(1), and two equivalent F(3) atoms to form distorted LiO3F3 octahedra that share  a cornercorner with one Li(2)O3F3 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(3)O3F3 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with three equivalent Li(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 0-17°. The Li(2)-O(1) bond length is 2.29 Å. The Li(2)-O(2) bond length is 2.33 Å. The Li(2)-O(3) bond length is 2.47 Å. The Li(2)-F(1) bond length is 1.93 Å. Both Li(2)-F(3) bond lengths are 1.99 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(4), one F(2), and two equivalent F(3) atoms to form distorted LiO3F3 octahedra that share  a cornercorner with one Li(3)O3F3 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Li(2)O3F3 octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with three equivalent Li(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 0-16°. The Li(3)-O(1) bond length is 2.37 Å. The Li(3)-O(2) bond length is 2.25 Å. The Li(3)-O(4) bond length is 2.45 Å. The Li(3)-F(2) bond length is 1.94 Å. There is one shorter (1.98 Å) and one longer (2.01 Å) Li(3)-F(3) bond length. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O3F3 octahedra, corners with four equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-16°. Both V(1)-O(1) bond lengths are 2.03 Å. Both V(1)-O(2) bond lengths are 2.02 Å. Both V(1)-O(3) bond lengths are 2.10 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent Li(3)O3F3 octahedra, corners with four equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-17°. Both V(2)-O(1) bond lengths are 2.02 Å. Both V(2)-O(2) bond lengths are 2.03 Å. Both V(2)-O(4) bond lengths are 2.11 Å. In the third V site, V(3) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O3F3 octahedra,  an edgeedge with one Li(1)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-17°. The V(3)-O(1) bond length is 1.98 Å. The V(3)-O(2) bond length is 2.05 Å. There is one shorter (1.88 Å) and one longer (2.04 Å) V(3)-O(3) bond length. There is one shorter (1.93 Å) and one longer (1.99 Å) V(3)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one O(3)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid, corners with two equivalent O(1)Li2V3 square pyramids, corners with two equivalent F(3)Li5 trigonal bipyramids, edges with three equivalent O(2)Li3V3 octahedra, edges with two equivalent O(3)Li2V3 square pyramids, edges with two equivalent O(4)Li2V3 square pyramids, and  an edgeedge with one F(3)Li5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 5°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with two equivalent O(2)Li3V3 octahedra,  a cornercorner with one O(1)Li2V3 square pyramid, corners with three equivalent F(3)Li5 trigonal bipyramids, edges with three equivalent O(1)Li2V3 square pyramids, edges with three equivalent O(3)Li2V3 square pyramids, edges with three equivalent O(4)Li2V3 square pyramids, and  an edgeedge with one F(3)Li5 trigonal bipyramid. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Li(1), one Li(2), one V(1), and two equivalent V(3) atoms to form distorted OLi2V3 square pyramids that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(3)Li2V3 square pyramid, corners with three equivalent O(4)Li2V3 square pyramids,  a cornercorner with one F(3)Li5 trigonal bipyramid, edges with three equivalent O(2)Li3V3 octahedra,  an edgeedge with one O(3)Li2V3 square pyramid,  an edgeedge with one O(4)Li2V3 square pyramid, edges with two equivalent O(1)Li2V3 square pyramids, and  an edgeedge with one F(3)Li5 trigonal bipyramid. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(2), and two equivalent V(3) atoms to form distorted OLi2V3 square pyramids that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid, corners with three equivalent O(3)Li2V3 square pyramids,  a cornercorner with one F(3)Li5 trigonal bipyramid, edges with three equivalent O(2)Li3V3 octahedra,  an edgeedge with one O(3)Li2V3 square pyramid,  an edgeedge with one O(4)Li2V3 square pyramid, edges with two equivalent O(1)Li2V3 square pyramids, and  an edgeedge with one F(3)Li5 trigonal bipyramid. There are three inequivalent F sites. In the first F site, F(1) is bonded in a square co-planar geometry to two equivalent Li(1) and two equivalent Li(2) 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(3) atoms. In the third F site, F(3) is bonded to one Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form FLi5 trigonal bipyramids that share corners with three equivalent O(2)Li3V3 octahedra,  a cornercorner with one O(3)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid, corners with two equivalent O(1)Li2V3 square pyramids,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(3)Li2V3 square pyramid,  an edgeedge with one O(4)Li2V3 square pyramid, and edges with two equivalent F(3)Li5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 12-18°.