Li3V2(OF)4 crystallizes in the monoclinic Pm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(3), one F(1), and one F(2) atom. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), one F(3), and one F(4) atom to form distorted LiO3F2 trigonal bipyramids that share  a cornercorner with one V(1)O4F2 octahedra, corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent Li(2)O3F2 trigonal bipyramids, and  an edgeedge with one V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 22-68°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(2), one F(2), two equivalent F(3), and two equivalent F(4) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(4), two equivalent O(1), one F(3), and one F(4) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(2)O3F2 trigonal bipyramid, edges with two equivalent V(2)O4F2 octahedra, and  an edgeedge with one Li(2)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 32°. In the second V site, V(2) is bonded to one O(1), one O(2), two equivalent O(4), one F(1), and one F(2) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent Li(2)O3F2 trigonal bipyramids, and edges with two equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 27°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), two equivalent Li(2), and one V(2) atom. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), and one V(1) atom to form OLi3V trigonal pyramids that share corners with two equivalent F(4)Li3V tetrahedra and corners with two equivalent O(3)Li3V trigonal pyramids. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(1) and two equivalent V(2) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Li(1) and one V(2) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(3), and one V(2) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Li(3), and one V(1) atom. In the fourth F site, F(4) is bonded to one Li(2), two equivalent Li(3), and one V(1) atom to form distorted FLi3V tetrahedra that share corners with two equivalent F(4)Li3V tetrahedra and corners with two equivalent O(3)Li3V trigonal pyramids.
Li3V2(OF)4 crystallizes in the monoclinic Pm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(3), one F(1), and one F(2) atom. The Li(1)-O(2) bond length is 2.54 Å. Both Li(1)-O(3) bond lengths are 2.09 Å. The Li(1)-F(1) bond length is 1.83 Å. The Li(1)-F(2) bond length is 1.86 Å. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), one F(3), and one F(4) atom to form distorted LiO3F2 trigonal bipyramids that share  a cornercorner with one V(1)O4F2 octahedra, corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent Li(2)O3F2 trigonal bipyramids, and  an edgeedge with one V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 22-68°. The Li(2)-O(3) bond length is 2.23 Å. Both Li(2)-O(2) bond lengths are 1.95 Å. The Li(2)-F(3) bond length is 1.90 Å. The Li(2)-F(4) bond length is 2.15 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(2), one F(2), two equivalent F(3), and two equivalent F(4) atoms. The Li(3)-O(2) bond length is 2.53 Å. The Li(3)-F(2) bond length is 1.84 Å. Both Li(3)-F(3) bond lengths are 2.39 Å. Both Li(3)-F(4) bond lengths are 2.17 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(4), two equivalent O(1), one F(3), and one F(4) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(2)O3F2 trigonal bipyramid, edges with two equivalent V(2)O4F2 octahedra, and  an edgeedge with one Li(2)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 32°. The V(1)-O(3) bond length is 1.68 Å. The V(1)-O(4) bond length is 2.31 Å. Both V(1)-O(1) bond lengths are 1.88 Å. The V(1)-F(3) bond length is 1.99 Å. The V(1)-F(4) bond length is 2.00 Å. In the second V site, V(2) is bonded to one O(1), one O(2), two equivalent O(4), one F(1), and one F(2) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent Li(2)O3F2 trigonal bipyramids, and edges with two equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 27°. The V(2)-O(1) bond length is 2.24 Å. The V(2)-O(2) bond length is 1.70 Å. Both V(2)-O(4) bond lengths are 1.86 Å. The V(2)-F(1) bond length is 1.86 Å. The V(2)-F(2) bond length is 1.98 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), two equivalent Li(2), and one V(2) atom. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), and one V(1) atom to form OLi3V trigonal pyramids that share corners with two equivalent F(4)Li3V tetrahedra and corners with two equivalent O(3)Li3V trigonal pyramids. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(1) and two equivalent V(2) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Li(1) and one V(2) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(3), and one V(2) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Li(3), and one V(1) atom. In the fourth F site, F(4) is bonded to one Li(2), two equivalent Li(3), and one V(1) atom to form distorted FLi3V tetrahedra that share corners with two equivalent F(4)Li3V tetrahedra and corners with two equivalent O(3)Li3V trigonal pyramids.