LiFeF4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to one F(3) and two equivalent F(2) atoms. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one F(4) and two equivalent F(1) atoms. Fe(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles range from 27-48°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(2) and one Fe(1) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Li(1) and one Fe(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Li(2) and two equivalent Fe(1) atoms. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to two equivalent Fe(1) atoms.
LiFeF4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to one F(3) and two equivalent F(2) atoms. The Li(1)-F(3) bond length is 1.96 Å. Both Li(1)-F(2) bond lengths are 1.88 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one F(4) and two equivalent F(1) atoms. The Li(2)-F(4) bond length is 2.32 Å. Both Li(2)-F(1) bond lengths are 1.87 Å. Fe(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles range from 27-48°. The Fe(1)-F(1) bond length is 1.88 Å. The Fe(1)-F(2) bond length is 1.90 Å. The Fe(1)-F(3) bond length is 2.06 Å. The Fe(1)-F(4) bond length is 2.03 Å. There is one shorter (1.96 Å) and one longer (2.00 Å) Fe(1)-F(5) bond length. There are five inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(2) and one Fe(1) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Li(1) and one Fe(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Li(2) and two equivalent Fe(1) atoms. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to two equivalent Fe(1) atoms.