Li3FeF6 crystallizes in the trigonal P-31m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent F(1) atoms to form LiF6 octahedra that share corners with six equivalent Fe(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and edges with three equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 44°. In the second Li site, Li(2) is bonded to six equivalent F(1) atoms to form LiF6 octahedra that share edges with six equivalent Li(1)F6 octahedra and faces with two equivalent Fe(1)F6 octahedra. Fe(1) is bonded to six equivalent F(1) atoms to form FeF6 octahedra that share corners with twelve equivalent Li(1)F6 octahedra and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 44°. F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Fe(1) atom.
Li3FeF6 crystallizes in the trigonal P-31m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent F(1) atoms to form LiF6 octahedra that share corners with six equivalent Fe(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and edges with three equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 44°. All Li(1)-F(1) bond lengths are 2.10 Å. In the second Li site, Li(2) is bonded to six equivalent F(1) atoms to form LiF6 octahedra that share edges with six equivalent Li(1)F6 octahedra and faces with two equivalent Fe(1)F6 octahedra. All Li(2)-F(1) bond lengths are 1.94 Å. Fe(1) is bonded to six equivalent F(1) atoms to form FeF6 octahedra that share corners with twelve equivalent Li(1)F6 octahedra and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 44°. All Fe(1)-F(1) bond lengths are 1.99 Å. F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Fe(1) atom.