NaAlF4 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded in a 6-coordinate geometry to six equivalent F(1) atoms. Al(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. There are three inequivalent F sites. In the first F site, F(1) is bonded to three equivalent Na(1) and one Al(1) atom to form a mixture of distorted corner and edge-sharing FNa3Al tetrahedra. In the second F site, F(2) is bonded in a linear geometry to two equivalent Al(1) atoms. In the third F site, F(3) is bonded in a linear geometry to two equivalent Al(1) atoms.
NaAlF4 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded in a 6-coordinate geometry to six equivalent F(1) atoms. There are four shorter (2.30 Å) and two longer (2.34 Å) Na(1)-F(1) bond lengths. Al(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. Both Al(1)-F(1) bond lengths are 1.78 Å. Both Al(1)-F(2) bond lengths are 1.82 Å. Both Al(1)-F(3) bond lengths are 1.81 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to three equivalent Na(1) and one Al(1) atom to form a mixture of distorted corner and edge-sharing FNa3Al tetrahedra. In the second F site, F(2) is bonded in a linear geometry to two equivalent Al(1) atoms. In the third F site, F(3) is bonded in a linear geometry to two equivalent Al(1) atoms.