Li3AlF6 crystallizes in the cubic Fm-3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to twelve equivalent F(1) atoms to form distorted LiF12 cuboctahedra that share corners with twelve equivalent Li(1)F12 cuboctahedra, faces with six equivalent Li(1)F12 cuboctahedra, faces with four equivalent Li(2)F6 octahedra, and faces with four equivalent Al(1)F6 octahedra. In the second Li site, Li(2) is bonded to six equivalent F(1) atoms to form LiF6 octahedra that share corners with six equivalent Al(1)F6 octahedra and faces with eight equivalent Li(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. Al(1) is bonded to six equivalent F(1) atoms to form AlF6 octahedra that share corners with six equivalent Li(2)F6 octahedra and faces with eight equivalent Li(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. F(1) is bonded in a linear geometry to one Li(2), four equivalent Li(1), and one Al(1) atom.
Li3AlF6 crystallizes in the cubic Fm-3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to twelve equivalent F(1) atoms to form distorted LiF12 cuboctahedra that share corners with twelve equivalent Li(1)F12 cuboctahedra, faces with six equivalent Li(1)F12 cuboctahedra, faces with four equivalent Li(2)F6 octahedra, and faces with four equivalent Al(1)F6 octahedra. All Li(1)-F(1) bond lengths are 2.61 Å. In the second Li site, Li(2) is bonded to six equivalent F(1) atoms to form LiF6 octahedra that share corners with six equivalent Al(1)F6 octahedra and faces with eight equivalent Li(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. All Li(2)-F(1) bond lengths are 1.90 Å. Al(1) is bonded to six equivalent F(1) atoms to form AlF6 octahedra that share corners with six equivalent Li(2)F6 octahedra and faces with eight equivalent Li(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. All Al(1)-F(1) bond lengths are 1.78 Å. F(1) is bonded in a linear geometry to one Li(2), four equivalent Li(1), and one Al(1) atom.