Li3V2(O2F)2 crystallizes in the monoclinic Pm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(4), one F(1), one F(2), and one F(3) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(5), one F(1), one F(2), and one F(3) atom. In the third Li site, Li(3) is bonded to one O(4), one F(2), and two equivalent F(1) atoms to form distorted LiOF3 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Li(4)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 23-78°. In the fourth Li site, Li(4) is bonded to one O(5), one F(3), and two equivalent F(1) atoms to form distorted LiOF3 tetrahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 23-78°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(3)OF3 tetrahedra,  a cornercorner with one Li(4)OF3 tetrahedra, 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. In the second V site, V(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one Li(3)OF3 tetrahedra, edges with two equivalent V(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. In the third V site, V(3) is bonded to one O(5), one O(6), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one Li(4)OF3 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one V(1), one V(2), and one V(3) atom to form distorted OLiV3 trigonal pyramids that share  a cornercorner with one F(2)Li5 trigonal bipyramid,  a cornercorner with one F(3)Li5 trigonal bipyramid, corners with two equivalent O(1)LiV3 trigonal pyramids, corners with three equivalent O(2)LiV3 trigonal pyramids,  an edgeedge with one O(4)Li3V3 octahedra, and  an edgeedge with one O(2)LiV3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(2), and one V(3) atom to form distorted OLiV3 trigonal pyramids that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one F(2)Li5 trigonal bipyramid,  a cornercorner with one F(3)Li5 trigonal bipyramid, corners with two equivalent O(2)LiV3 trigonal pyramids, corners with three equivalent O(1)LiV3 trigonal pyramids,  an edgeedge with one O(4)Li3V3 octahedra, and  an edgeedge with one O(1)LiV3 trigonal pyramid. The corner-sharing octahedral tilt angles are 83°. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(2) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Li(1), one V(2), and two equivalent V(1) atoms to form distorted OLi3V3 octahedra that share  a cornercorner with one F(2)Li5 trigonal bipyramid, corners with two equivalent F(3)Li5 trigonal bipyramids, corners with two equivalent O(2)LiV3 trigonal pyramids,  an edgeedge with one F(2)Li5 trigonal bipyramid, edges with two equivalent O(1)LiV3 trigonal pyramids, and edges with two equivalent O(2)LiV3 trigonal pyramids. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Li(4), two equivalent Li(2), one V(3), and two equivalent V(1) atoms. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(3) and two equivalent V(1) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a square co-planar geometry to one Li(1), one Li(2), one Li(3), and one Li(4) atom. In the second F site, F(2) is bonded to one Li(3), two equivalent Li(1), and two equivalent Li(2) atoms to form distorted FLi5 trigonal bipyramids that share  a cornercorner with one O(4)Li3V3 octahedra, corners with two equivalent O(1)LiV3 trigonal pyramids, corners with two equivalent O(2)LiV3 trigonal pyramids,  an edgeedge with one O(4)Li3V3 octahedra, and edges with two equivalent F(3)Li5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 33°. In the third F site, F(3) is bonded to one Li(4), two equivalent Li(1), and two equivalent Li(2) atoms to form distorted FLi5 trigonal bipyramids that share corners with two equivalent O(4)Li3V3 octahedra, corners with two equivalent O(1)LiV3 trigonal pyramids, corners with two equivalent O(2)LiV3 trigonal pyramids, and edges with two equivalent F(2)Li5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 14°.
Li3V2(O2F)2 crystallizes in the monoclinic Pm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(4), one F(1), one F(2), and one F(3) atom. The Li(1)-O(2) bond length is 2.07 Å. The Li(1)-O(4) bond length is 2.54 Å. The Li(1)-F(1) bond length is 1.95 Å. The Li(1)-F(2) bond length is 2.00 Å. The Li(1)-F(3) bond length is 2.01 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(5), one F(1), one F(2), and one F(3) atom. The Li(2)-O(1) bond length is 2.07 Å. The Li(2)-O(5) bond length is 2.55 Å. The Li(2)-F(1) bond length is 1.94 Å. The Li(2)-F(2) bond length is 2.00 Å. The Li(2)-F(3) bond length is 2.00 Å. In the third Li site, Li(3) is bonded to one O(4), one F(2), and two equivalent F(1) atoms to form distorted LiOF3 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Li(4)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 23-78°. The Li(3)-O(4) bond length is 2.05 Å. The Li(3)-F(2) bond length is 1.92 Å. Both Li(3)-F(1) bond lengths are 1.88 Å. In the fourth Li site, Li(4) is bonded to one O(5), one F(3), and two equivalent F(1) atoms to form distorted LiOF3 tetrahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 23-78°. The Li(4)-O(5) bond length is 2.05 Å. The Li(4)-F(3) bond length is 1.92 Å. Both Li(4)-F(1) bond lengths are 1.88 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(3)OF3 tetrahedra,  a cornercorner with one Li(4)OF3 tetrahedra, 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 V(1)-O(1) bond length is 2.02 Å. The V(1)-O(2) bond length is 2.02 Å. The V(1)-O(3) bond length is 2.04 Å. The V(1)-O(4) bond length is 2.10 Å. The V(1)-O(5) bond length is 2.10 Å. The V(1)-O(6) bond length is 2.04 Å. In the second V site, V(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one Li(3)OF3 tetrahedra, edges with two equivalent V(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The V(2)-O(3) bond length is 1.88 Å. The V(2)-O(4) bond length is 1.92 Å. Both V(2)-O(1) bond lengths are 2.00 Å. Both V(2)-O(2) bond lengths are 2.03 Å. In the third V site, V(3) is bonded to one O(5), one O(6), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one Li(4)OF3 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The V(3)-O(5) bond length is 1.92 Å. The V(3)-O(6) bond length is 1.88 Å. Both V(3)-O(1) bond lengths are 2.03 Å. Both V(3)-O(2) bond lengths are 2.00 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one V(1), one V(2), and one V(3) atom to form distorted OLiV3 trigonal pyramids that share  a cornercorner with one F(2)Li5 trigonal bipyramid,  a cornercorner with one F(3)Li5 trigonal bipyramid, corners with two equivalent O(1)LiV3 trigonal pyramids, corners with three equivalent O(2)LiV3 trigonal pyramids,  an edgeedge with one O(4)Li3V3 octahedra, and  an edgeedge with one O(2)LiV3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(2), and one V(3) atom to form distorted OLiV3 trigonal pyramids that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one F(2)Li5 trigonal bipyramid,  a cornercorner with one F(3)Li5 trigonal bipyramid, corners with two equivalent O(2)LiV3 trigonal pyramids, corners with three equivalent O(1)LiV3 trigonal pyramids,  an edgeedge with one O(4)Li3V3 octahedra, and  an edgeedge with one O(1)LiV3 trigonal pyramid. The corner-sharing octahedral tilt angles are 83°. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(2) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Li(1), one V(2), and two equivalent V(1) atoms to form distorted OLi3V3 octahedra that share  a cornercorner with one F(2)Li5 trigonal bipyramid, corners with two equivalent F(3)Li5 trigonal bipyramids, corners with two equivalent O(2)LiV3 trigonal pyramids,  an edgeedge with one F(2)Li5 trigonal bipyramid, edges with two equivalent O(1)LiV3 trigonal pyramids, and edges with two equivalent O(2)LiV3 trigonal pyramids. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Li(4), two equivalent Li(2), one V(3), and two equivalent V(1) atoms. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(3) and two equivalent V(1) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a square co-planar geometry to one Li(1), one Li(2), one Li(3), and one Li(4) atom. In the second F site, F(2) is bonded to one Li(3), two equivalent Li(1), and two equivalent Li(2) atoms to form distorted FLi5 trigonal bipyramids that share  a cornercorner with one O(4)Li3V3 octahedra, corners with two equivalent O(1)LiV3 trigonal pyramids, corners with two equivalent O(2)LiV3 trigonal pyramids,  an edgeedge with one O(4)Li3V3 octahedra, and edges with two equivalent F(3)Li5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 33°. In the third F site, F(3) is bonded to one Li(4), two equivalent Li(1), and two equivalent Li(2) atoms to form distorted FLi5 trigonal bipyramids that share corners with two equivalent O(4)Li3V3 octahedra, corners with two equivalent O(1)LiV3 trigonal pyramids, corners with two equivalent O(2)LiV3 trigonal pyramids, and edges with two equivalent F(2)Li5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 14°.