LiFeF3 is beta indium sulfide-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one F(1), one F(2), and two equivalent F(4) atoms. In the second Li site, Li(2) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra, edges with two equivalent Fe(1)F6 octahedra, and edges with two equivalent Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles are 28°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms to form distorted FeF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Fe(2)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, and edges with two equivalent Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 9-28°. In the second Fe site, Fe(2) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form FeF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra,  an edgeedge with one Fe(2)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, and edges with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles are 9°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(1), and two equivalent Fe(2) atoms. In the second F site, F(2) is bonded to one Li(1), two equivalent Li(2), and one Fe(1) atom to form distorted edge-sharing FLi3Fe tetrahedra. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(2), one Fe(1), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Fe(1), and one Fe(2) atom.
LiFeF3 is beta indium sulfide-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one F(1), one F(2), and two equivalent F(4) atoms. The Li(1)-F(1) bond length is 1.96 Å. The Li(1)-F(2) bond length is 1.84 Å. Both Li(1)-F(4) bond lengths are 2.01 Å. In the second Li site, Li(2) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra, edges with two equivalent Fe(1)F6 octahedra, and edges with two equivalent Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles are 28°. Both Li(2)-F(2) bond lengths are 2.01 Å. Both Li(2)-F(3) bond lengths are 1.96 Å. Both Li(2)-F(4) bond lengths are 2.44 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms to form distorted FeF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Fe(2)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, and edges with two equivalent Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 9-28°. The Fe(1)-F(1) bond length is 2.29 Å. The Fe(1)-F(2) bond length is 2.05 Å. Both Fe(1)-F(3) bond lengths are 2.06 Å. Both Fe(1)-F(4) bond lengths are 2.14 Å. In the second Fe site, Fe(2) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form FeF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra,  an edgeedge with one Fe(2)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, and edges with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles are 9°. Both Fe(2)-F(1) bond lengths are 2.12 Å. Both Fe(2)-F(3) bond lengths are 2.08 Å. Both Fe(2)-F(4) bond lengths are 2.11 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(1), and two equivalent Fe(2) atoms. In the second F site, F(2) is bonded to one Li(1), two equivalent Li(2), and one Fe(1) atom to form distorted edge-sharing FLi3Fe tetrahedra. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(2), one Fe(1), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Fe(1), and one Fe(2) atom.