LiFeF3 crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted square co-planar geometry to four equivalent F(2) atoms. In the second Li site, Li(2) is bonded in a square co-planar geometry to two equivalent F(1) and two equivalent F(3) 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 edge and corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles are 65°. 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 to two equivalent Li(1) and two equivalent Fe(1) atoms to form a mixture of edge and corner-sharing FLi2Fe2 tetrahedra. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Fe(1) atoms.
LiFeF3 crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted square co-planar geometry to four equivalent F(2) atoms. All Li(1)-F(2) bond lengths are 2.15 Å. In the second Li site, Li(2) is bonded in a square co-planar geometry to two equivalent F(1) and two equivalent F(3) atoms. Both Li(2)-F(1) bond lengths are 1.88 Å. Both Li(2)-F(3) bond lengths are 1.92 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 edge and corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles are 65°. Both Fe(1)-F(1) bond lengths are 2.10 Å. There is one shorter (2.14 Å) and one longer (2.17 Å) Fe(1)-F(2) bond length. Both Fe(1)-F(3) bond lengths are 2.09 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 to two equivalent Li(1) and two equivalent Fe(1) atoms to form a mixture of edge and corner-sharing FLi2Fe2 tetrahedra. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Fe(1) atoms.