Li2VF6 is beta Vanadium nitride-derived structured and crystallizes in the monoclinic C2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(8) atom to form LiF6 octahedra that share corners with four equivalent V(1)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one V(2)F6 octahedra, and edges with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-48°. In the second Li site, Li(2) is bonded to one F(2), one F(4), one F(5), one F(7), one F(8), and one F(9) atom to form LiF6 octahedra that share corners with four equivalent V(1)F6 octahedra,  an edgeedge with one Li(4)F6 octahedra,  an edgeedge with one V(2)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-48°. In the third Li site, Li(3) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(6) atoms to form LiF6 octahedra that share corners with four equivalent V(1)F6 octahedra,  an edgeedge with one Li(4)F6 octahedra,  an edgeedge with one V(2)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-47°. In the fourth Li site, Li(4) is bonded to two equivalent F(6), two equivalent F(7), and two equivalent F(9) atoms to form LiF6 octahedra that share corners with four equivalent V(1)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one V(2)F6 octahedra, and edges with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-47°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one F(2), one F(3), one F(5), one F(6), one F(7), and one F(8) atom to form VF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(4)F6 octahedra, corners with four equivalent Li(1)F6 octahedra, and corners with four equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-48°. In the second V site, V(2) is bonded to two equivalent F(1), two equivalent F(4), and two equivalent F(9) atoms to form VF6 octahedra that share  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Li(4)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and edges with two equivalent Li(2)F6 octahedra. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(3), and one V(2) atom. In the second F site, F(2) is bonded in a distorted T-shaped 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 one Li(1), one Li(3), and one V(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(2) 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(3), one Li(4), and one V(1) atom. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Li(2), one Li(4), and one V(1) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the ninth F site, F(9) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Li(4), and one V(2) atom.
Li2VF6 is beta Vanadium nitride-derived structured and crystallizes in the monoclinic C2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(8) atom to form LiF6 octahedra that share corners with four equivalent V(1)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one V(2)F6 octahedra, and edges with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-48°. The Li(1)-F(1) bond length is 2.06 Å. The Li(1)-F(2) bond length is 2.04 Å. The Li(1)-F(3) bond length is 2.15 Å. The Li(1)-F(4) bond length is 2.03 Å. The Li(1)-F(5) bond length is 2.08 Å. The Li(1)-F(8) bond length is 2.05 Å. In the second Li site, Li(2) is bonded to one F(2), one F(4), one F(5), one F(7), one F(8), and one F(9) atom to form LiF6 octahedra that share corners with four equivalent V(1)F6 octahedra,  an edgeedge with one Li(4)F6 octahedra,  an edgeedge with one V(2)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-48°. The Li(2)-F(2) bond length is 2.04 Å. The Li(2)-F(4) bond length is 2.03 Å. The Li(2)-F(5) bond length is 2.08 Å. The Li(2)-F(7) bond length is 2.15 Å. The Li(2)-F(8) bond length is 2.04 Å. The Li(2)-F(9) bond length is 2.06 Å. In the third Li site, Li(3) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(6) atoms to form LiF6 octahedra that share corners with four equivalent V(1)F6 octahedra,  an edgeedge with one Li(4)F6 octahedra,  an edgeedge with one V(2)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-47°. Both Li(3)-F(1) bond lengths are 2.05 Å. Both Li(3)-F(3) bond lengths are 2.14 Å. Both Li(3)-F(6) bond lengths are 2.00 Å. In the fourth Li site, Li(4) is bonded to two equivalent F(6), two equivalent F(7), and two equivalent F(9) atoms to form LiF6 octahedra that share corners with four equivalent V(1)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one V(2)F6 octahedra, and edges with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-47°. Both Li(4)-F(6) bond lengths are 2.00 Å. Both Li(4)-F(7) bond lengths are 2.14 Å. Both Li(4)-F(9) bond lengths are 2.05 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one F(2), one F(3), one F(5), one F(6), one F(7), and one F(8) atom to form VF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(4)F6 octahedra, corners with four equivalent Li(1)F6 octahedra, and corners with four equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-48°. The V(1)-F(2) bond length is 1.89 Å. The V(1)-F(3) bond length is 1.86 Å. The V(1)-F(5) bond length is 1.90 Å. The V(1)-F(6) bond length is 1.93 Å. The V(1)-F(7) bond length is 1.87 Å. The V(1)-F(8) bond length is 1.89 Å. In the second V site, V(2) is bonded to two equivalent F(1), two equivalent F(4), and two equivalent F(9) atoms to form VF6 octahedra that share  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Li(4)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and edges with two equivalent Li(2)F6 octahedra. Both V(2)-F(1) bond lengths are 1.87 Å. Both V(2)-F(4) bond lengths are 1.89 Å. Both V(2)-F(9) bond lengths are 1.88 Å. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(3), and one V(2) atom. In the second F site, F(2) is bonded in a distorted T-shaped 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 one Li(1), one Li(3), and one V(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(2) 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(3), one Li(4), and one V(1) atom. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Li(2), one Li(4), and one V(1) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the ninth F site, F(9) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Li(4), and one V(2) atom.