MnAlF5 crystallizes in the orthorhombic Cmcm space group. Mn(1) is bonded to two equivalent F(3) and four equivalent F(2) atoms to form MnF6 octahedra that share corners with six equivalent Al(1)F6 octahedra and edges with two equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 13-55°. 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 Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 8-55°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent Al(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to two equivalent Mn(1) and one Al(1) atom. In the third F site, F(3) is bonded in a linear geometry to one Mn(1) and one Al(1) atom.
MnAlF5 crystallizes in the orthorhombic Cmcm space group. Mn(1) is bonded to two equivalent F(3) and four equivalent F(2) atoms to form MnF6 octahedra that share corners with six equivalent Al(1)F6 octahedra and edges with two equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 13-55°. Both Mn(1)-F(3) bond lengths are 2.01 Å. All Mn(1)-F(2) bond lengths are 2.22 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 Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 8-55°. Both Al(1)-F(1) bond lengths are 1.79 Å. Both Al(1)-F(2) bond lengths are 1.83 Å. Both Al(1)-F(3) bond lengths are 1.77 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent Al(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to two equivalent Mn(1) and one Al(1) atom. In the third F site, F(3) is bonded in a linear geometry to one Mn(1) and one Al(1) atom.