Li2VF6 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form distorted LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(2)F5 trigonal bipyramids, and  an edgeedge with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles are 65°. In the second Li site, Li(2) is bonded to one F(2), one F(4), one F(5), and two equivalent F(6) atoms to form distorted LiF5 trigonal bipyramids that share corners with two equivalent Li(1)F6 octahedra and corners with two equivalent Li(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 63-72°. V(1) is bonded in a 7-coordinate geometry to one F(1), one F(2), one F(3), one F(4), one F(6), and two equivalent F(5) atoms. There are six inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom. 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 in a distorted T-shaped geometry to two equivalent Li(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar 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 trigonal planar geometry to one Li(2) and two equivalent V(1) atoms. In the sixth F site, F(6) is bonded in a trigonal planar geometry to two equivalent Li(2) and one V(1) atom.
Li2VF6 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form distorted LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(2)F5 trigonal bipyramids, and  an edgeedge with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles are 65°. The Li(1)-F(2) bond length is 2.33 Å. The Li(1)-F(4) bond length is 2.03 Å. There is one shorter (2.00 Å) and one longer (2.02 Å) Li(1)-F(1) bond length. There is one shorter (2.02 Å) and one longer (2.19 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), and two equivalent F(6) atoms to form distorted LiF5 trigonal bipyramids that share corners with two equivalent Li(1)F6 octahedra and corners with two equivalent Li(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 63-72°. The Li(2)-F(2) bond length is 2.01 Å. The Li(2)-F(4) bond length is 2.06 Å. The Li(2)-F(5) bond length is 1.98 Å. There is one shorter (1.93 Å) and one longer (2.01 Å) Li(2)-F(6) bond length. V(1) is bonded in a 7-coordinate geometry to one F(1), one F(2), one F(3), one F(4), one F(6), and two equivalent F(5) atoms. The V(1)-F(1) bond length is 1.96 Å. The V(1)-F(2) bond length is 1.90 Å. The V(1)-F(3) bond length is 1.88 Å. The V(1)-F(4) bond length is 1.90 Å. The V(1)-F(6) bond length is 1.92 Å. There is one shorter (1.95 Å) and one longer (2.33 Å) V(1)-F(5) bond length. There are six inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom. 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 in a distorted T-shaped geometry to two equivalent Li(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar 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 trigonal planar geometry to one Li(2) and two equivalent V(1) atoms. In the sixth F site, F(6) is bonded in a trigonal planar geometry to two equivalent Li(2) and one V(1) atom.