FeAlF5 crystallizes in the orthorhombic Immm space group. Fe(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form FeF6 octahedra that share corners with six equivalent Al(1)F6 octahedra and edges with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-54°. Al(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form AlF6 octahedra that share corners with two equivalent Al(1)F6 octahedra and corners with six equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-54°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Fe(1) and one Al(1) atom. In the second F site, F(2) is bonded in a linear geometry to one Fe(1) and one Al(1) atom. In the third F site, F(3) is bonded in a linear geometry to two equivalent Al(1) atoms. In the fourth F site, F(1) is bonded in a trigonal planar geometry to two equivalent Fe(1) and one Al(1) atom.
FeAlF5 crystallizes in the orthorhombic Immm space group. Fe(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form FeF6 octahedra that share corners with six equivalent Al(1)F6 octahedra and edges with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-54°. Both Fe(1)-F(2) bond lengths are 1.93 Å. All Fe(1)-F(1) bond lengths are 2.18 Å. Al(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form AlF6 octahedra that share corners with two equivalent Al(1)F6 octahedra and corners with six equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-54°. Both Al(1)-F(1) bond lengths are 1.82 Å. Both Al(1)-F(2) bond lengths are 1.79 Å. Both Al(1)-F(3) bond lengths are 1.78 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Fe(1) and one Al(1) atom. Both F(1)-Fe(1) bond lengths are 2.18 Å. In the second F site, F(2) is bonded in a linear geometry to one Fe(1) and one Al(1) atom. In the third F site, F(3) is bonded in a linear geometry to two equivalent Al(1) atoms. In the fourth F site, F(1) is bonded in a trigonal planar geometry to two equivalent Fe(1) and one Al(1) atom. The F(1)-Al(1) bond length is 1.82 Å.