LiFeF4 is Hydrophilite-derived structured and crystallizes in the orthorhombic Pbcn space group. Li(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with six equivalent Fe(1)F6 octahedra, and  an edgeedge with one Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. Fe(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form FeF6 octahedra that share corners with six equivalent Li(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and edges with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Fe(1) atom.
LiFeF4 is Hydrophilite-derived structured and crystallizes in the orthorhombic Pbcn space group. Li(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with six equivalent Fe(1)F6 octahedra, and  an edgeedge with one Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. Both Li(1)-F(1) bond lengths are 2.15 Å. There are two shorter (2.11 Å) and two longer (2.13 Å) Li(1)-F(2) bond lengths. Fe(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form FeF6 octahedra that share corners with six equivalent Li(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and edges with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. Both Fe(1)-F(2) bond lengths are 1.88 Å. There are two shorter (1.99 Å) and two longer (2.06 Å) Fe(1)-F(1) bond lengths. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Fe(1) atom.