LiFeF3 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to two equivalent F(1) and two equivalent F(3) atoms to form LiF4 trigonal pyramids that share corners with four equivalent Fe(1)F6 octahedra, corners with four equivalent Li(1)F4 trigonal pyramids, and  an edgeedge with one Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 12-74°. Fe(1) is bonded to one F(1), two equivalent F(3), and three equivalent F(2) atoms to form FeF6 octahedra that share corners with four equivalent Li(1)F4 trigonal pyramids, edges with four equivalent Fe(1)F6 octahedra, and  an edgeedge with one Li(1)F4 trigonal pyramid. There are three inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Fe(1) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Fe(1) atoms.
LiFeF3 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to two equivalent F(1) and two equivalent F(3) atoms to form LiF4 trigonal pyramids that share corners with four equivalent Fe(1)F6 octahedra, corners with four equivalent Li(1)F4 trigonal pyramids, and  an edgeedge with one Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 12-74°. There is one shorter (1.90 Å) and one longer (1.91 Å) Li(1)-F(1) bond length. Both Li(1)-F(3) bond lengths are 2.06 Å. Fe(1) is bonded to one F(1), two equivalent F(3), and three equivalent F(2) atoms to form FeF6 octahedra that share corners with four equivalent Li(1)F4 trigonal pyramids, edges with four equivalent Fe(1)F6 octahedra, and  an edgeedge with one Li(1)F4 trigonal pyramid. The Fe(1)-F(1) bond length is 1.97 Å. Both Fe(1)-F(3) bond lengths are 2.14 Å. There is one shorter (2.06 Å) and two longer (2.18 Å) Fe(1)-F(2) bond lengths. There are three inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Fe(1) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Fe(1) atoms.