Li2VF7 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms to form distorted LiF7 pentagonal bipyramids that share corners with three equivalent V(1)F6 octahedra, corners with two equivalent Li(1)F7 pentagonal bipyramids, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 28-52°. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(1), one F(2), one F(3), and two equivalent F(5) atoms. V(1) is bonded to one F(1), one F(2), two equivalent F(4), and two equivalent F(5) atoms to form VF6 octahedra that share corners with three equivalent Li(1)F7 pentagonal bipyramids and  an edgeedge with one Li(1)F7 pentagonal bipyramid. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Li(1), one Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Li(2) and one V(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(2) and two equivalent Li(1) atoms. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one V(1) atom.
Li2VF7 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms to form distorted LiF7 pentagonal bipyramids that share corners with three equivalent V(1)F6 octahedra, corners with two equivalent Li(1)F7 pentagonal bipyramids, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 28-52°. The Li(1)-F(1) bond length is 2.47 Å. There is one shorter (1.88 Å) and one longer (1.90 Å) Li(1)-F(3) bond length. Both Li(1)-F(4) bond lengths are 2.38 Å. Both Li(1)-F(5) bond lengths are 2.44 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(1), one F(2), one F(3), and two equivalent F(5) atoms. The Li(2)-F(1) bond length is 1.99 Å. The Li(2)-F(2) bond length is 1.96 Å. The Li(2)-F(3) bond length is 1.84 Å. Both Li(2)-F(5) bond lengths are 2.37 Å. V(1) is bonded to one F(1), one F(2), two equivalent F(4), and two equivalent F(5) atoms to form VF6 octahedra that share corners with three equivalent Li(1)F7 pentagonal bipyramids and  an edgeedge with one Li(1)F7 pentagonal bipyramid. The V(1)-F(1) bond length is 1.84 Å. The V(1)-F(2) bond length is 1.82 Å. Both V(1)-F(4) bond lengths are 1.79 Å. Both V(1)-F(5) bond lengths are 1.83 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Li(1), one Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Li(2) and one V(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(2) and two equivalent Li(1) atoms. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one V(1) atom.