LiFeF3 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to four equivalent F(3) atoms. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to two equivalent F(1) and two equivalent F(2) atoms. Fe(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form a mixture of corner and edge-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles are 64°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Fe(1) atoms. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Li(2) and two equivalent Fe(1) atoms. In the third F site, F(3) is bonded to two equivalent Li(1) and two equivalent Fe(1) atoms to form a mixture of corner and edge-sharing FLi2Fe2 tetrahedra.
LiFeF3 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to four equivalent F(3) atoms. There are two shorter (2.15 Å) and two longer (2.17 Å) Li(1)-F(3) bond lengths. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to two equivalent F(1) and two equivalent F(2) atoms. Both Li(2)-F(1) bond lengths are 1.90 Å. Both Li(2)-F(2) bond lengths are 1.90 Å. Fe(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form a mixture of corner and edge-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles are 64°. Both Fe(1)-F(1) bond lengths are 2.08 Å. Both Fe(1)-F(2) bond lengths are 2.10 Å. Both Fe(1)-F(3) bond lengths are 2.14 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Fe(1) atoms. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Li(2) and two equivalent Fe(1) atoms. In the third F site, F(3) is bonded to two equivalent Li(1) and two equivalent Fe(1) atoms to form a mixture of corner and edge-sharing FLi2Fe2 tetrahedra.