Li2VF4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal planar geometry to one F(1), one F(2), and one F(4) atom. In the second Li site, Li(2) is bonded to one F(2), two equivalent F(1), and two equivalent F(3) atoms to form distorted LiF5 square pyramids that share corners with five equivalent V(1)F6 octahedra,  an edgeedge with one V(1)F6 octahedra, and edges with two equivalent Li(2)F5 square pyramids. The corner-sharing octahedral tilt angles range from 49-58°. V(1) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms to form VF6 octahedra that share corners with five equivalent Li(2)F5 square pyramids, edges with two equivalent V(1)F6 octahedra, and  an edgeedge with one Li(2)F5 square pyramid. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form distorted FLi3V trigonal pyramids that share corners with four equivalent F(3)Li2V2 trigonal pyramids,  an edgeedge with one F(3)Li2V2 trigonal pyramid, and  an edgeedge with one F(1)Li3V trigonal pyramid. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one V(1) atom. In the third F site, F(3) is bonded to two equivalent Li(2) and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share corners with two equivalent F(3)Li2V2 trigonal pyramids, corners with four equivalent F(1)Li3V trigonal pyramids,  an edgeedge with one F(3)Li2V2 trigonal pyramid, and  an edgeedge with one F(1)Li3V trigonal pyramid. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Li(1) and two equivalent V(1) atoms.
Li2VF4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal planar geometry to one F(1), one F(2), and one F(4) atom. The Li(1)-F(1) bond length is 1.89 Å. The Li(1)-F(2) bond length is 1.87 Å. The Li(1)-F(4) bond length is 1.88 Å. In the second Li site, Li(2) is bonded to one F(2), two equivalent F(1), and two equivalent F(3) atoms to form distorted LiF5 square pyramids that share corners with five equivalent V(1)F6 octahedra,  an edgeedge with one V(1)F6 octahedra, and edges with two equivalent Li(2)F5 square pyramids. The corner-sharing octahedral tilt angles range from 49-58°. The Li(2)-F(2) bond length is 1.92 Å. There is one shorter (1.94 Å) and one longer (2.20 Å) Li(2)-F(1) bond length. There is one shorter (2.05 Å) and one longer (2.14 Å) Li(2)-F(3) bond length. V(1) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms to form VF6 octahedra that share corners with five equivalent Li(2)F5 square pyramids, edges with two equivalent V(1)F6 octahedra, and  an edgeedge with one Li(2)F5 square pyramid. The V(1)-F(1) bond length is 2.12 Å. The V(1)-F(2) bond length is 2.09 Å. There is one shorter (2.14 Å) and one longer (2.15 Å) V(1)-F(3) bond length. Both V(1)-F(4) bond lengths are 2.11 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form distorted FLi3V trigonal pyramids that share corners with four equivalent F(3)Li2V2 trigonal pyramids,  an edgeedge with one F(3)Li2V2 trigonal pyramid, and  an edgeedge with one F(1)Li3V trigonal pyramid. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one V(1) atom. In the third F site, F(3) is bonded to two equivalent Li(2) and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share corners with two equivalent F(3)Li2V2 trigonal pyramids, corners with four equivalent F(1)Li3V trigonal pyramids,  an edgeedge with one F(3)Li2V2 trigonal pyramid, and  an edgeedge with one F(1)Li3V trigonal pyramid. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Li(1) and two equivalent V(1) atoms.