LiV2OF5 is Hydrophilite-derived structured and crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(2), one F(3), one F(5), one F(6), and one F(8) atom to form LiOF5 octahedra that share corners with two equivalent V(1)OF5 octahedra, corners with two equivalent V(3)OF5 octahedra, corners with two equivalent V(6)OF5 octahedra,  an edgeedge with one V(2)OF5 octahedra,  an edgeedge with one V(4)OF5 octahedra, and  an edgeedge with one V(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. In the second Li site, Li(2) is bonded to one O(3), one F(1), one F(11), one F(15), one F(4), and one F(7) atom to form LiOF5 octahedra that share corners with two equivalent V(2)OF5 octahedra, corners with two equivalent V(4)OF5 octahedra, corners with two equivalent V(5)OF5 octahedra,  an edgeedge with one V(1)OF5 octahedra,  an edgeedge with one V(3)OF5 octahedra, and  an edgeedge with one V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. In the third Li site, Li(3) is bonded to one O(2), one F(10), one F(12), one F(13), one F(14), and one F(9) atom to form LiOF5 octahedra that share corners with two equivalent V(1)OF5 octahedra, corners with two equivalent V(3)OF5 octahedra, corners with two equivalent V(6)OF5 octahedra,  an edgeedge with one V(2)OF5 octahedra,  an edgeedge with one V(4)OF5 octahedra, and  an edgeedge with one V(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(11), one F(12), one F(14), and one F(2) atom to form VOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(3)OF5 octahedra, corners with two equivalent V(2)OF5 octahedra, corners with two equivalent V(4)OF5 octahedra, corners with two equivalent V(5)OF5 octahedra, and  an edgeedge with one Li(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-55°. In the second V site, V(2) is bonded to one O(1), one F(13), one F(14), one F(15), one F(4), and one F(5) atom to form VOF5 octahedra that share corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent V(1)OF5 octahedra, corners with two equivalent V(3)OF5 octahedra, corners with two equivalent V(6)OF5 octahedra,  an edgeedge with one Li(1)OF5 octahedra, and  an edgeedge with one Li(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-52°. In the third V site, V(3) is bonded to one O(2), one F(4), one F(5), one F(7), one F(8), and one F(9) atom to form VOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(3)OF5 octahedra, corners with two equivalent V(2)OF5 octahedra, corners with two equivalent V(4)OF5 octahedra, corners with two equivalent V(5)OF5 octahedra, and  an edgeedge with one Li(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-55°. In the fourth V site, V(4) is bonded to one O(2), one F(1), one F(10), one F(2), one F(3), and one F(7) atom to form VOF5 octahedra that share corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent V(1)OF5 octahedra, corners with two equivalent V(3)OF5 octahedra, corners with two equivalent V(6)OF5 octahedra,  an edgeedge with one Li(1)OF5 octahedra, and  an edgeedge with one Li(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. In the fifth V site, V(5) is bonded to one O(3), one F(11), one F(12), one F(6), one F(8), and one F(9) atom to form VOF5 octahedra that share corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent V(1)OF5 octahedra, corners with two equivalent V(3)OF5 octahedra, corners with two equivalent V(6)OF5 octahedra,  an edgeedge with one Li(1)OF5 octahedra, and  an edgeedge with one Li(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. In the sixth V site, V(6) is bonded to one O(3), one F(10), one F(13), one F(15), one F(3), and one F(6) atom to form VOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(3)OF5 octahedra, corners with two equivalent V(2)OF5 octahedra, corners with two equivalent V(4)OF5 octahedra, corners with two equivalent V(5)OF5 octahedra, and  an edgeedge with one Li(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(3), one V(3), and one V(4) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(2), one V(5), and one V(6) atom. There are fifteen inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(4) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(4) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(4), and one V(6) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(3) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one V(3) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(5), and one V(6) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(2), one V(3), and one V(4) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Li(1), one V(3), and one V(5) atom. In the ninth F site, F(9) is bonded in a distorted trigonal planar geometry to one Li(3), one V(3), and one V(5) atom. In the tenth F site, F(10) is bonded in a distorted T-shaped geometry to one Li(3), one V(4), and one V(6) atom. In the eleventh F site, F(11) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(5) atom. In the twelfth F site, F(12) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(5) atom. In the thirteenth F site, F(13) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one V(6) atom. In the fourteenth F site, F(14) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(2) atom. In the fifteenth F site, F(15) is bonded in a distorted T-shaped geometry to one Li(2), one V(2), and one V(6) atom.
LiV2OF5 is Hydrophilite-derived structured and crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(2), one F(3), one F(5), one F(6), and one F(8) atom to form LiOF5 octahedra that share corners with two equivalent V(1)OF5 octahedra, corners with two equivalent V(3)OF5 octahedra, corners with two equivalent V(6)OF5 octahedra,  an edgeedge with one V(2)OF5 octahedra,  an edgeedge with one V(4)OF5 octahedra, and  an edgeedge with one V(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. The Li(1)-O(1) bond length is 2.07 Å. The Li(1)-F(2) bond length is 2.09 Å. The Li(1)-F(3) bond length is 2.01 Å. The Li(1)-F(5) bond length is 2.05 Å. The Li(1)-F(6) bond length is 2.05 Å. The Li(1)-F(8) bond length is 2.05 Å. In the second Li site, Li(2) is bonded to one O(3), one F(1), one F(11), one F(15), one F(4), and one F(7) atom to form LiOF5 octahedra that share corners with two equivalent V(2)OF5 octahedra, corners with two equivalent V(4)OF5 octahedra, corners with two equivalent V(5)OF5 octahedra,  an edgeedge with one V(1)OF5 octahedra,  an edgeedge with one V(3)OF5 octahedra, and  an edgeedge with one V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. The Li(2)-O(3) bond length is 2.06 Å. The Li(2)-F(1) bond length is 2.01 Å. The Li(2)-F(11) bond length is 2.07 Å. The Li(2)-F(15) bond length is 2.02 Å. The Li(2)-F(4) bond length is 2.04 Å. The Li(2)-F(7) bond length is 2.03 Å. In the third Li site, Li(3) is bonded to one O(2), one F(10), one F(12), one F(13), one F(14), and one F(9) atom to form LiOF5 octahedra that share corners with two equivalent V(1)OF5 octahedra, corners with two equivalent V(3)OF5 octahedra, corners with two equivalent V(6)OF5 octahedra,  an edgeedge with one V(2)OF5 octahedra,  an edgeedge with one V(4)OF5 octahedra, and  an edgeedge with one V(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. The Li(3)-O(2) bond length is 2.07 Å. The Li(3)-F(10) bond length is 2.05 Å. The Li(3)-F(12) bond length is 2.04 Å. The Li(3)-F(13) bond length is 2.06 Å. The Li(3)-F(14) bond length is 2.03 Å. The Li(3)-F(9) bond length is 2.07 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(11), one F(12), one F(14), and one F(2) atom to form VOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(3)OF5 octahedra, corners with two equivalent V(2)OF5 octahedra, corners with two equivalent V(4)OF5 octahedra, corners with two equivalent V(5)OF5 octahedra, and  an edgeedge with one Li(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-55°. The V(1)-O(1) bond length is 1.85 Å. The V(1)-F(1) bond length is 2.08 Å. The V(1)-F(11) bond length is 2.11 Å. The V(1)-F(12) bond length is 2.03 Å. The V(1)-F(14) bond length is 2.06 Å. The V(1)-F(2) bond length is 2.02 Å. In the second V site, V(2) is bonded to one O(1), one F(13), one F(14), one F(15), one F(4), and one F(5) atom to form VOF5 octahedra that share corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent V(1)OF5 octahedra, corners with two equivalent V(3)OF5 octahedra, corners with two equivalent V(6)OF5 octahedra,  an edgeedge with one Li(1)OF5 octahedra, and  an edgeedge with one Li(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-52°. The V(2)-O(1) bond length is 1.86 Å. The V(2)-F(13) bond length is 2.03 Å. The V(2)-F(14) bond length is 2.05 Å. The V(2)-F(15) bond length is 2.06 Å. The V(2)-F(4) bond length is 2.06 Å. The V(2)-F(5) bond length is 2.03 Å. In the third V site, V(3) is bonded to one O(2), one F(4), one F(5), one F(7), one F(8), and one F(9) atom to form VOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(3)OF5 octahedra, corners with two equivalent V(2)OF5 octahedra, corners with two equivalent V(4)OF5 octahedra, corners with two equivalent V(5)OF5 octahedra, and  an edgeedge with one Li(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-55°. The V(3)-O(2) bond length is 1.86 Å. The V(3)-F(4) bond length is 2.03 Å. The V(3)-F(5) bond length is 2.10 Å. The V(3)-F(7) bond length is 2.07 Å. The V(3)-F(8) bond length is 2.08 Å. The V(3)-F(9) bond length is 2.02 Å. In the fourth V site, V(4) is bonded to one O(2), one F(1), one F(10), one F(2), one F(3), and one F(7) atom to form VOF5 octahedra that share corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent V(1)OF5 octahedra, corners with two equivalent V(3)OF5 octahedra, corners with two equivalent V(6)OF5 octahedra,  an edgeedge with one Li(1)OF5 octahedra, and  an edgeedge with one Li(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. The V(4)-O(2) bond length is 1.86 Å. The V(4)-F(1) bond length is 2.02 Å. The V(4)-F(10) bond length is 2.04 Å. The V(4)-F(2) bond length is 2.08 Å. The V(4)-F(3) bond length is 2.05 Å. The V(4)-F(7) bond length is 2.03 Å. In the fifth V site, V(5) is bonded to one O(3), one F(11), one F(12), one F(6), one F(8), and one F(9) atom to form VOF5 octahedra that share corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent V(1)OF5 octahedra, corners with two equivalent V(3)OF5 octahedra, corners with two equivalent V(6)OF5 octahedra,  an edgeedge with one Li(1)OF5 octahedra, and  an edgeedge with one Li(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. The V(5)-O(3) bond length is 1.85 Å. The V(5)-F(11) bond length is 2.00 Å. The V(5)-F(12) bond length is 2.07 Å. The V(5)-F(6) bond length is 2.07 Å. The V(5)-F(8) bond length is 2.02 Å. The V(5)-F(9) bond length is 2.11 Å. In the sixth V site, V(6) is bonded to one O(3), one F(10), one F(13), one F(15), one F(3), and one F(6) atom to form VOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(3)OF5 octahedra, corners with two equivalent V(2)OF5 octahedra, corners with two equivalent V(4)OF5 octahedra, corners with two equivalent V(5)OF5 octahedra, and  an edgeedge with one Li(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. The V(6)-O(3) bond length is 1.86 Å. The V(6)-F(10) bond length is 2.06 Å. The V(6)-F(13) bond length is 2.06 Å. The V(6)-F(15) bond length is 2.06 Å. The V(6)-F(3) bond length is 2.04 Å. The V(6)-F(6) bond length is 2.04 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(3), one V(3), and one V(4) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(2), one V(5), and one V(6) atom. There are fifteen inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(4) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(4) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(4), and one V(6) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(3) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one V(3) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(5), and one V(6) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(2), one V(3), and one V(4) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Li(1), one V(3), and one V(5) atom. In the ninth F site, F(9) is bonded in a distorted trigonal planar geometry to one Li(3), one V(3), and one V(5) atom. In the tenth F site, F(10) is bonded in a distorted T-shaped geometry to one Li(3), one V(4), and one V(6) atom. In the eleventh F site, F(11) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(5) atom. In the twelfth F site, F(12) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(5) atom. In the thirteenth F site, F(13) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one V(6) atom. In the fourteenth F site, F(14) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(2) atom. In the fifteenth F site, F(15) is bonded in a distorted T-shaped geometry to one Li(2), one V(2), and one V(6) atom.