Li2FeF5 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(10), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form LiF6 octahedra that share corners with two equivalent Li(4)F6 octahedra, corners with two equivalent Li(2)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra, edges with two equivalent Fe(1)F6 octahedra, and edges with two equivalent Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 59-61°. In the second Li site, Li(2) is bonded to one F(1), one F(3), one F(4), and one F(7) atom to form LiF4 tetrahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(4)F6 octahedra, corners with two equivalent Fe(2)F6 octahedra, and corners with three equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-79°. In the third Li site, Li(3) is bonded to one F(2), one F(6), one F(8), and one F(9) atom to form LiF4 tetrahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(4)F6 octahedra, corners with two equivalent Fe(1)F6 octahedra, and corners with three equivalent Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-79°. In the fourth Li site, Li(4) is bonded to one F(1), one F(10), one F(5), one F(7), one F(8), and one F(9) atom to form LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with three equivalent Fe(1)F6 octahedra, corners with three equivalent Fe(2)F6 octahedra, corners with two equivalent Li(2)F4 tetrahedra, and corners with two equivalent Li(3)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-61°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(1), one F(10), one F(3), one F(4), one F(6), and one F(8) atom to form FeF6 octahedra that share corners with three equivalent Li(4)F6 octahedra, corners with two equivalent Li(3)F4 tetrahedra, corners with three equivalent Li(2)F4 tetrahedra,  an edgeedge with one Fe(2)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-49°. In the second Fe site, Fe(2) is bonded to one F(2), one F(3), one F(5), one F(6), one F(7), and one F(9) atom to form FeF6 octahedra that share corners with three equivalent Li(4)F6 octahedra, corners with two equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(3)F4 tetrahedra,  an edgeedge with one Fe(1)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-49°. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(4), and one Fe(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(3), and one Fe(2) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Fe(1), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Fe(1) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one Li(4), and one Fe(2) atom. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Fe(1), and one Fe(2) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(4), and one Fe(2) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(4), and one Fe(1) atom. In the ninth F site, F(9) is bonded in a trigonal planar geometry to one Li(3), one Li(4), and one Fe(2) atom. In the tenth F site, F(10) is bonded in a trigonal planar geometry to one Li(1), one Li(4), and one Fe(1) atom.
Li2FeF5 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(10), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form LiF6 octahedra that share corners with two equivalent Li(4)F6 octahedra, corners with two equivalent Li(2)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra, edges with two equivalent Fe(1)F6 octahedra, and edges with two equivalent Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 59-61°. The Li(1)-F(10) bond length is 2.06 Å. The Li(1)-F(2) bond length is 1.98 Å. The Li(1)-F(3) bond length is 2.18 Å. The Li(1)-F(4) bond length is 1.99 Å. The Li(1)-F(5) bond length is 2.06 Å. The Li(1)-F(6) bond length is 2.18 Å. In the second Li site, Li(2) is bonded to one F(1), one F(3), one F(4), and one F(7) atom to form LiF4 tetrahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(4)F6 octahedra, corners with two equivalent Fe(2)F6 octahedra, and corners with three equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-79°. The Li(2)-F(1) bond length is 1.93 Å. The Li(2)-F(3) bond length is 1.99 Å. The Li(2)-F(4) bond length is 1.89 Å. The Li(2)-F(7) bond length is 1.92 Å. In the third Li site, Li(3) is bonded to one F(2), one F(6), one F(8), and one F(9) atom to form LiF4 tetrahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(4)F6 octahedra, corners with two equivalent Fe(1)F6 octahedra, and corners with three equivalent Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-79°. The Li(3)-F(2) bond length is 1.88 Å. The Li(3)-F(6) bond length is 1.99 Å. The Li(3)-F(8) bond length is 1.93 Å. The Li(3)-F(9) bond length is 1.93 Å. In the fourth Li site, Li(4) is bonded to one F(1), one F(10), one F(5), one F(7), one F(8), and one F(9) atom to form LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with three equivalent Fe(1)F6 octahedra, corners with three equivalent Fe(2)F6 octahedra, corners with two equivalent Li(2)F4 tetrahedra, and corners with two equivalent Li(3)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-61°. The Li(4)-F(1) bond length is 2.12 Å. The Li(4)-F(10) bond length is 2.00 Å. The Li(4)-F(5) bond length is 2.00 Å. The Li(4)-F(7) bond length is 2.38 Å. The Li(4)-F(8) bond length is 2.28 Å. The Li(4)-F(9) bond length is 2.10 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(1), one F(10), one F(3), one F(4), one F(6), and one F(8) atom to form FeF6 octahedra that share corners with three equivalent Li(4)F6 octahedra, corners with two equivalent Li(3)F4 tetrahedra, corners with three equivalent Li(2)F4 tetrahedra,  an edgeedge with one Fe(2)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-49°. The Fe(1)-F(1) bond length is 1.91 Å. The Fe(1)-F(10) bond length is 1.93 Å. The Fe(1)-F(3) bond length is 2.12 Å. The Fe(1)-F(4) bond length is 1.92 Å. The Fe(1)-F(6) bond length is 2.08 Å. The Fe(1)-F(8) bond length is 1.92 Å. In the second Fe site, Fe(2) is bonded to one F(2), one F(3), one F(5), one F(6), one F(7), and one F(9) atom to form FeF6 octahedra that share corners with three equivalent Li(4)F6 octahedra, corners with two equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(3)F4 tetrahedra,  an edgeedge with one Fe(1)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-49°. The Fe(2)-F(2) bond length is 1.92 Å. The Fe(2)-F(3) bond length is 2.08 Å. The Fe(2)-F(5) bond length is 1.93 Å. The Fe(2)-F(6) bond length is 2.12 Å. The Fe(2)-F(7) bond length is 1.91 Å. The Fe(2)-F(9) bond length is 1.91 Å. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(4), and one Fe(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(3), and one Fe(2) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Fe(1), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Fe(1) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one Li(4), and one Fe(2) atom. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Fe(1), and one Fe(2) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(4), and one Fe(2) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(4), and one Fe(1) atom. In the ninth F site, F(9) is bonded in a trigonal planar geometry to one Li(3), one Li(4), and one Fe(2) atom. In the tenth F site, F(10) is bonded in a trigonal planar geometry to one Li(1), one Li(4), and one Fe(1) atom.