LiFeF3 crystallizes in the tetragonal P4_2/n space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 8-coordinate geometry to four equivalent F(1) and four equivalent F(3) atoms. In the second Li site, Li(2) is bonded to four equivalent F(1) atoms to form corner-sharing LiF4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. In the third Li site, Li(3) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form corner-sharing LiF6 octahedra. Fe(1) is bonded in a 6-coordinate geometry to one F(1), two equivalent F(3), and three equivalent F(2) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Fe(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(3) and three equivalent Fe(1) atoms. In the third F site, F(3) is bonded to one Li(1), one Li(3), and two equivalent Fe(1) atoms to form a mixture of distorted corner and edge-sharing FLi2Fe2 tetrahedra.
LiFeF3 crystallizes in the tetragonal P4_2/n space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 8-coordinate geometry to four equivalent F(1) and four equivalent F(3) atoms. All Li(1)-F(1) bond lengths are 2.53 Å. All Li(1)-F(3) bond lengths are 2.41 Å. In the second Li site, Li(2) is bonded to four equivalent F(1) atoms to form corner-sharing LiF4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. All Li(2)-F(1) bond lengths are 1.84 Å. In the third Li site, Li(3) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form corner-sharing LiF6 octahedra. Both Li(3)-F(1) bond lengths are 1.99 Å. Both Li(3)-F(2) bond lengths are 2.03 Å. Both Li(3)-F(3) bond lengths are 2.11 Å. Fe(1) is bonded in a 6-coordinate geometry to one F(1), two equivalent F(3), and three equivalent F(2) atoms. The Fe(1)-F(1) bond length is 1.98 Å. There is one shorter (2.10 Å) and one longer (2.11 Å) Fe(1)-F(3) bond length. There are a spread of Fe(1)-F(2) bond distances ranging from 2.02-2.64 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Fe(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(3) and three equivalent Fe(1) atoms. In the third F site, F(3) is bonded to one Li(1), one Li(3), and two equivalent Fe(1) atoms to form a mixture of distorted corner and edge-sharing FLi2Fe2 tetrahedra.