Li2VF5 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 6-coordinate geometry to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms. In the second Li site, Li(2) is bonded to one F(5), two equivalent F(3), and two equivalent F(4) atoms to form distorted LiF5 trigonal bipyramids that share corners with three equivalent V(1)F7 pentagonal bipyramids,  an edgeedge with one V(1)F7 pentagonal bipyramid, and edges with two equivalent Li(2)F5 trigonal bipyramids. V(1) is bonded to one F(3), one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms to form distorted VF7 pentagonal bipyramids that share corners with three equivalent Li(2)F5 trigonal bipyramids, edges with two equivalent V(1)F7 pentagonal bipyramids, and  an edgeedge with one Li(2)F5 trigonal bipyramid. There are five inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share corners with four equivalent F(4)Li3V tetrahedra, corners with two equivalent F(1)Li2V2 trigonal pyramids, corners with two equivalent F(2)Li2V2 trigonal pyramids, corners with two equivalent F(3)Li3V trigonal pyramids,  an edgeedge with one F(1)Li2V2 trigonal pyramid,  an edgeedge with one F(3)Li3V trigonal pyramid, and edges with three equivalent F(2)Li2V2 trigonal pyramids. In the second F site, F(2) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share corners with two equivalent F(4)Li3V tetrahedra, corners with two equivalent F(1)Li2V2 trigonal pyramids, corners with two equivalent F(2)Li2V2 trigonal pyramids, corners with four equivalent F(3)Li3V trigonal pyramids,  an edgeedge with one F(4)Li3V tetrahedra,  an edgeedge with one F(2)Li2V2 trigonal pyramid, and edges with three equivalent F(1)Li2V2 trigonal pyramids. In the third F site, F(3) 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 two equivalent F(4)Li3V tetrahedra, corners with two equivalent F(1)Li2V2 trigonal pyramids, corners with four equivalent F(2)Li2V2 trigonal pyramids, edges with two equivalent F(4)Li3V tetrahedra,  an edgeedge with one F(1)Li2V2 trigonal pyramid, and  an edgeedge with one F(3)Li3V trigonal pyramid. In the fourth F site, F(4) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form distorted FLi3V tetrahedra that share corners with two equivalent F(2)Li2V2 trigonal pyramids, corners with two equivalent F(3)Li3V trigonal pyramids, corners with four equivalent F(1)Li2V2 trigonal pyramids,  an edgeedge with one F(4)Li3V tetrahedra,  an edgeedge with one F(2)Li2V2 trigonal pyramid, and edges with two equivalent F(3)Li3V trigonal pyramids. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom.
Li2VF5 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 6-coordinate geometry to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms. The Li(1)-F(3) bond length is 2.00 Å. The Li(1)-F(4) bond length is 1.96 Å. There is one shorter (2.01 Å) and one longer (2.21 Å) Li(1)-F(1) bond length. There is one shorter (2.12 Å) and one longer (2.22 Å) Li(1)-F(2) bond length. In the second Li site, Li(2) is bonded to one F(5), two equivalent F(3), and two equivalent F(4) atoms to form distorted LiF5 trigonal bipyramids that share corners with three equivalent V(1)F7 pentagonal bipyramids,  an edgeedge with one V(1)F7 pentagonal bipyramid, and edges with two equivalent Li(2)F5 trigonal bipyramids. The Li(2)-F(5) bond length is 1.87 Å. There is one shorter (2.02 Å) and one longer (2.03 Å) Li(2)-F(3) bond length. There is one shorter (1.99 Å) and one longer (2.03 Å) Li(2)-F(4) bond length. V(1) is bonded to one F(3), one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms to form distorted VF7 pentagonal bipyramids that share corners with three equivalent Li(2)F5 trigonal bipyramids, edges with two equivalent V(1)F7 pentagonal bipyramids, and  an edgeedge with one Li(2)F5 trigonal bipyramid. The V(1)-F(3) bond length is 2.01 Å. The V(1)-F(4) bond length is 2.02 Å. The V(1)-F(5) bond length is 1.89 Å. There is one shorter (2.10 Å) and one longer (2.16 Å) V(1)-F(1) bond length. There is one shorter (2.08 Å) and one longer (2.16 Å) V(1)-F(2) bond length. There are five inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share corners with four equivalent F(4)Li3V tetrahedra, corners with two equivalent F(1)Li2V2 trigonal pyramids, corners with two equivalent F(2)Li2V2 trigonal pyramids, corners with two equivalent F(3)Li3V trigonal pyramids,  an edgeedge with one F(1)Li2V2 trigonal pyramid,  an edgeedge with one F(3)Li3V trigonal pyramid, and edges with three equivalent F(2)Li2V2 trigonal pyramids. In the second F site, F(2) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share corners with two equivalent F(4)Li3V tetrahedra, corners with two equivalent F(1)Li2V2 trigonal pyramids, corners with two equivalent F(2)Li2V2 trigonal pyramids, corners with four equivalent F(3)Li3V trigonal pyramids,  an edgeedge with one F(4)Li3V tetrahedra,  an edgeedge with one F(2)Li2V2 trigonal pyramid, and edges with three equivalent F(1)Li2V2 trigonal pyramids. In the third F site, F(3) 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 two equivalent F(4)Li3V tetrahedra, corners with two equivalent F(1)Li2V2 trigonal pyramids, corners with four equivalent F(2)Li2V2 trigonal pyramids, edges with two equivalent F(4)Li3V tetrahedra,  an edgeedge with one F(1)Li2V2 trigonal pyramid, and  an edgeedge with one F(3)Li3V trigonal pyramid. In the fourth F site, F(4) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form distorted FLi3V tetrahedra that share corners with two equivalent F(2)Li2V2 trigonal pyramids, corners with two equivalent F(3)Li3V trigonal pyramids, corners with four equivalent F(1)Li2V2 trigonal pyramids,  an edgeedge with one F(4)Li3V tetrahedra,  an edgeedge with one F(2)Li2V2 trigonal pyramid, and edges with two equivalent F(3)Li3V trigonal pyramids. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom.