Li2V2F7 crystallizes in the monoclinic P2_1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one F(2), one F(5), one F(6), and two equivalent F(3) atoms. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(4), one F(5), one F(7), and one F(9) atom to form LiF6 octahedra that share corners with two equivalent V(2)F6 octahedra, corners with two equivalent V(4)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one V(2)F6 octahedra, and  an edgeedge with one V(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. In the third Li site, Li(3) is bonded to one F(10), one F(11), one F(14), one F(2), one F(4), and one F(6) atom to form distorted LiF6 octahedra that share corners with two equivalent V(2)F6 octahedra, corners with two equivalent V(4)F6 octahedra, corners with two equivalent Li(4)F4 tetrahedra,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one V(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. In the fourth Li site, Li(4) is bonded to one F(11), one F(6), and two equivalent F(13) atoms to form distorted LiF4 tetrahedra that share corners with two equivalent Li(3)F6 octahedra, corners with three equivalent V(3)F6 octahedra, and corners with two equivalent Li(4)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-76°. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 7-coordinate geometry to one F(11), one F(13), one F(2), one F(6), one F(8), and two equivalent F(3) atoms. In the second V site, V(2) is bonded to one F(10), one F(12), one F(4), one F(7), and two equivalent F(1) atoms to form VF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent V(2)F6 octahedra, corners with two equivalent V(4)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one V(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. In the third V site, V(3) is bonded to one F(11), one F(13), one F(14), one F(5), one F(8), and one F(9) atom to form VF6 octahedra that share corners with two equivalent V(4)F6 octahedra, corners with three equivalent Li(4)F4 tetrahedra,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. In the fourth V site, V(4) is bonded to one F(10), one F(14), one F(7), one F(9), and two equivalent F(12) atoms to form VF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent V(2)F6 octahedra, corners with two equivalent V(3)F6 octahedra, corners with two equivalent V(4)F6 octahedra, and  an edgeedge with one V(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-60°. There are fourteen inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent V(2) atoms. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to two equivalent Li(1) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one V(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(3) atom. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Li(4), and one V(1) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(4) atom. In the eighth F site, F(8) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(3) atom. In the ninth F site, F(9) is bonded in a distorted T-shaped geometry to one Li(2), one V(3), and one V(4) atom. In the tenth F site, F(10) is bonded in a trigonal planar geometry to one Li(3), one V(2), and one V(4) atom. In the eleventh F site, F(11) is bonded in a 3-coordinate geometry to one Li(3), one Li(4), one V(1), and one V(3) atom. In the twelfth F site, F(12) is bonded in a trigonal planar geometry to one V(2) and two equivalent V(4) atoms. In the thirteenth F site, F(13) is bonded to two equivalent Li(4), one V(1), and one V(3) atom to form distorted corner-sharing FLi2V2 tetrahedra. In the fourteenth F site, F(14) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one V(4) atom.
Li2V2F7 crystallizes in the monoclinic P2_1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one F(2), one F(5), one F(6), and two equivalent F(3) atoms. The Li(1)-F(2) bond length is 1.89 Å. The Li(1)-F(5) bond length is 1.92 Å. The Li(1)-F(6) bond length is 1.93 Å. There is one shorter (2.40 Å) and one longer (2.51 Å) Li(1)-F(3) bond length. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(4), one F(5), one F(7), and one F(9) atom to form LiF6 octahedra that share corners with two equivalent V(2)F6 octahedra, corners with two equivalent V(4)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one V(2)F6 octahedra, and  an edgeedge with one V(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. The Li(2)-F(1) bond length is 2.03 Å. The Li(2)-F(2) bond length is 2.06 Å. The Li(2)-F(4) bond length is 1.99 Å. The Li(2)-F(5) bond length is 1.94 Å. The Li(2)-F(7) bond length is 2.21 Å. The Li(2)-F(9) bond length is 2.09 Å. In the third Li site, Li(3) is bonded to one F(10), one F(11), one F(14), one F(2), one F(4), and one F(6) atom to form distorted LiF6 octahedra that share corners with two equivalent V(2)F6 octahedra, corners with two equivalent V(4)F6 octahedra, corners with two equivalent Li(4)F4 tetrahedra,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one V(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. The Li(3)-F(10) bond length is 2.02 Å. The Li(3)-F(11) bond length is 1.99 Å. The Li(3)-F(14) bond length is 2.14 Å. The Li(3)-F(2) bond length is 2.08 Å. The Li(3)-F(4) bond length is 1.95 Å. The Li(3)-F(6) bond length is 2.38 Å. In the fourth Li site, Li(4) is bonded to one F(11), one F(6), and two equivalent F(13) atoms to form distorted LiF4 tetrahedra that share corners with two equivalent Li(3)F6 octahedra, corners with three equivalent V(3)F6 octahedra, and corners with two equivalent Li(4)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-76°. The Li(4)-F(11) bond length is 1.89 Å. The Li(4)-F(6) bond length is 1.86 Å. There is one shorter (1.94 Å) and one longer (2.08 Å) Li(4)-F(13) bond length. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 7-coordinate geometry to one F(11), one F(13), one F(2), one F(6), one F(8), and two equivalent F(3) atoms. The V(1)-F(11) bond length is 2.64 Å. The V(1)-F(13) bond length is 2.45 Å. The V(1)-F(2) bond length is 2.11 Å. The V(1)-F(6) bond length is 2.03 Å. The V(1)-F(8) bond length is 2.15 Å. There is one shorter (2.05 Å) and one longer (2.06 Å) V(1)-F(3) bond length. In the second V site, V(2) is bonded to one F(10), one F(12), one F(4), one F(7), and two equivalent F(1) atoms to form VF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent V(2)F6 octahedra, corners with two equivalent V(4)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one V(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. The V(2)-F(10) bond length is 2.02 Å. The V(2)-F(12) bond length is 2.07 Å. The V(2)-F(4) bond length is 1.96 Å. The V(2)-F(7) bond length is 1.99 Å. There is one shorter (2.05 Å) and one longer (2.08 Å) V(2)-F(1) bond length. In the third V site, V(3) is bonded to one F(11), one F(13), one F(14), one F(5), one F(8), and one F(9) atom to form VF6 octahedra that share corners with two equivalent V(4)F6 octahedra, corners with three equivalent Li(4)F4 tetrahedra,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. The V(3)-F(11) bond length is 1.99 Å. The V(3)-F(13) bond length is 2.04 Å. The V(3)-F(14) bond length is 2.02 Å. The V(3)-F(5) bond length is 1.94 Å. The V(3)-F(8) bond length is 1.95 Å. The V(3)-F(9) bond length is 2.03 Å. In the fourth V site, V(4) is bonded to one F(10), one F(14), one F(7), one F(9), and two equivalent F(12) atoms to form VF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent V(2)F6 octahedra, corners with two equivalent V(3)F6 octahedra, corners with two equivalent V(4)F6 octahedra, and  an edgeedge with one V(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-60°. The V(4)-F(10) bond length is 2.15 Å. The V(4)-F(14) bond length is 2.14 Å. The V(4)-F(7) bond length is 2.13 Å. The V(4)-F(9) bond length is 2.11 Å. There is one shorter (2.17 Å) and one longer (2.19 Å) V(4)-F(12) bond length. There are fourteen inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent V(2) atoms. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to two equivalent Li(1) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one V(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(3) atom. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Li(4), and one V(1) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(4) atom. In the eighth F site, F(8) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(3) atom. In the ninth F site, F(9) is bonded in a distorted T-shaped geometry to one Li(2), one V(3), and one V(4) atom. In the tenth F site, F(10) is bonded in a trigonal planar geometry to one Li(3), one V(2), and one V(4) atom. In the eleventh F site, F(11) is bonded in a 3-coordinate geometry to one Li(3), one Li(4), one V(1), and one V(3) atom. In the twelfth F site, F(12) is bonded in a trigonal planar geometry to one V(2) and two equivalent V(4) atoms. In the thirteenth F site, F(13) is bonded to two equivalent Li(4), one V(1), and one V(3) atom to form distorted corner-sharing FLi2V2 tetrahedra. In the fourteenth F site, F(14) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one V(4) atom.