Li2VF6 is Hydrophilite-derived structured and crystallizes in the orthorhombic Pna2_1 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(2), one F(4), one F(5), one F(6), and two equivalent F(3) atoms. In the second Li site, Li(2) is bonded to one F(2), one F(4), one F(5), one F(6), and two equivalent F(1) atoms to form LiF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with four equivalent V(1)F6 octahedra, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 36-52°. V(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form VF6 octahedra that share corners with four equivalent Li(2)F6 octahedra and  an edgeedge with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 36-51°. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(2) and one V(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one V(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom.
Li2VF6 is Hydrophilite-derived structured and crystallizes in the orthorhombic Pna2_1 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(2), one F(4), one F(5), one F(6), and two equivalent F(3) atoms. The Li(1)-F(2) bond length is 2.04 Å. The Li(1)-F(4) bond length is 1.92 Å. The Li(1)-F(5) bond length is 2.31 Å. The Li(1)-F(6) bond length is 2.04 Å. There is one shorter (1.88 Å) and one longer (1.90 Å) Li(1)-F(3) bond length. In the second Li site, Li(2) is bonded to one F(2), one F(4), one F(5), one F(6), and two equivalent F(1) atoms to form LiF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with four equivalent V(1)F6 octahedra, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 36-52°. The Li(2)-F(2) bond length is 1.90 Å. The Li(2)-F(4) bond length is 2.07 Å. The Li(2)-F(5) bond length is 1.97 Å. The Li(2)-F(6) bond length is 2.14 Å. There is one shorter (1.97 Å) and one longer (2.13 Å) Li(2)-F(1) bond length. V(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form VF6 octahedra that share corners with four equivalent Li(2)F6 octahedra and  an edgeedge with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 36-51°. The V(1)-F(1) bond length is 1.84 Å. The V(1)-F(2) bond length is 1.88 Å. The V(1)-F(3) bond length is 1.89 Å. The V(1)-F(4) bond length is 1.86 Å. The V(1)-F(5) bond length is 1.84 Å. The V(1)-F(6) bond length is 1.82 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(2) and one V(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one V(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom.