LiFeF4 is Hydrophilite-derived structured and crystallizes in the monoclinic Pc space group. There are two 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(7) atom to form distorted LiF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra, corners with two equivalent Fe(2)F6 octahedra, corners with four equivalent Li(2)F6 octahedra,  an edgeedge with one Fe(1)F6 octahedra, and  an edgeedge with one Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-58°. In the second Li site, Li(2) is bonded to one F(2), one F(4), one F(5), one F(6), one F(7), and one F(8) atom to form distorted LiF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra, corners with two equivalent Fe(2)F6 octahedra, corners with four equivalent Li(1)F6 octahedra,  an edgeedge with one Fe(1)F6 octahedra, and  an edgeedge with one Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-59°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(1), one F(2), one F(3), one F(6), one F(7), and one F(8) atom to form FeF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra, and edges with two equivalent Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-57°. In the second Fe site, Fe(2) is bonded to one F(1), one F(3), one F(4), one F(5), one F(6), and one F(8) atom to form FeF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra, and edges with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-59°. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one Fe(2) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Fe(1) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(1), one Fe(1), and one Fe(2) 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 Fe(2) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Fe(2) atom. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Li(2), 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(1), one Li(2), and one Fe(1) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Li(2), one Fe(1), and one Fe(2) atom.
LiFeF4 is Hydrophilite-derived structured and crystallizes in the monoclinic Pc space group. There are two 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(7) atom to form distorted LiF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra, corners with two equivalent Fe(2)F6 octahedra, corners with four equivalent Li(2)F6 octahedra,  an edgeedge with one Fe(1)F6 octahedra, and  an edgeedge with one Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-58°. The Li(1)-F(1) bond length is 2.05 Å. The Li(1)-F(2) bond length is 2.04 Å. The Li(1)-F(3) bond length is 2.30 Å. The Li(1)-F(4) bond length is 2.08 Å. The Li(1)-F(5) bond length is 2.20 Å. The Li(1)-F(7) bond length is 2.23 Å. In the second Li site, Li(2) is bonded to one F(2), one F(4), one F(5), one F(6), one F(7), and one F(8) atom to form distorted LiF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra, corners with two equivalent Fe(2)F6 octahedra, corners with four equivalent Li(1)F6 octahedra,  an edgeedge with one Fe(1)F6 octahedra, and  an edgeedge with one Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-59°. The Li(2)-F(2) bond length is 2.08 Å. The Li(2)-F(4) bond length is 2.39 Å. The Li(2)-F(5) bond length is 2.11 Å. The Li(2)-F(6) bond length is 2.31 Å. The Li(2)-F(7) bond length is 2.04 Å. The Li(2)-F(8) bond length is 2.02 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(1), one F(2), one F(3), one F(6), one F(7), and one F(8) atom to form FeF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra, and edges with two equivalent Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-57°. The Fe(1)-F(1) bond length is 2.02 Å. The Fe(1)-F(2) bond length is 1.91 Å. The Fe(1)-F(3) bond length is 1.99 Å. The Fe(1)-F(6) bond length is 1.99 Å. The Fe(1)-F(7) bond length is 1.90 Å. The Fe(1)-F(8) bond length is 2.02 Å. In the second Fe site, Fe(2) is bonded to one F(1), one F(3), one F(4), one F(5), one F(6), and one F(8) atom to form FeF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra, and edges with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-59°. The Fe(2)-F(1) bond length is 2.03 Å. The Fe(2)-F(3) bond length is 2.01 Å. The Fe(2)-F(4) bond length is 1.88 Å. The Fe(2)-F(5) bond length is 1.89 Å. The Fe(2)-F(6) bond length is 2.00 Å. The Fe(2)-F(8) bond length is 2.05 Å. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one Fe(2) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Fe(1) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(1), one Fe(1), and one Fe(2) 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 Fe(2) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Fe(2) atom. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Li(2), 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(1), one Li(2), and one Fe(1) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Li(2), one Fe(1), and one Fe(2) atom.