Li3Fe2F9 crystallizes in the hexagonal P-62c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to six equivalent F(2) atoms. In the second Li site, Li(2) is bonded in a trigonal planar geometry to three equivalent F(1) atoms. Fe(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted face-sharing FeF6 octahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar 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 two equivalent Li(1) and one Fe(1) atom.
Li3Fe2F9 crystallizes in the hexagonal P-62c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to six equivalent F(2) atoms. There are three shorter (1.96 Å) and three longer (2.47 Å) Li(1)-F(2) bond lengths. In the second Li site, Li(2) is bonded in a trigonal planar geometry to three equivalent F(1) atoms. All Li(2)-F(1) bond lengths are 1.85 Å. Fe(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted face-sharing FeF6 octahedra. All Fe(1)-F(1) bond lengths are 2.07 Å. All Fe(1)-F(2) bond lengths are 1.90 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar 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 two equivalent Li(1) and one Fe(1) atom.