Na2ZnAlF7 crystallizes in the orthorhombic Imma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent F(2), two equivalent F(3), and four equivalent F(1) atoms to form NaF8 hexagonal bipyramids that share corners with two equivalent Na(1)F8 hexagonal bipyramids, corners with two equivalent Al(1)F6 octahedra, edges with four equivalent Na(2)F8 hexagonal bipyramids, edges with two equivalent Al(1)F6 octahedra, and edges with four equivalent Zn(1)F6 octahedra. The corner-sharing octahedral tilt angles are 49°. In the second Na site, Na(2) is bonded to four equivalent F(1) and four equivalent F(2) atoms to form distorted NaF8 hexagonal bipyramids that share edges with two equivalent Na(2)F8 hexagonal bipyramids, edges with four equivalent Na(1)F8 hexagonal bipyramids, edges with two equivalent Zn(1)F6 octahedra, and edges with four equivalent Al(1)F6 octahedra. Zn(1) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form ZnF6 octahedra that share corners with two equivalent Zn(1)F6 octahedra, corners with four equivalent Al(1)F6 octahedra, edges with two equivalent Na(2)F8 hexagonal bipyramids, and edges with four equivalent Na(1)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 38-54°. Al(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form AlF6 octahedra that share corners with two equivalent Na(1)F8 hexagonal bipyramids, corners with four equivalent Zn(1)F6 octahedra, edges with two equivalent Na(1)F8 hexagonal bipyramids, and edges with four equivalent Na(2)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 38°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Zn(1), and one Al(1) atom. In the second F site, F(2) is bonded to one Na(1), two equivalent Na(2), and one Al(1) atom to form a mixture of distorted edge and corner-sharing FNa3Al tetrahedra. In the third F site, F(3) is bonded in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Zn(1) atoms.
Na2ZnAlF7 crystallizes in the orthorhombic Imma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent F(2), two equivalent F(3), and four equivalent F(1) atoms to form NaF8 hexagonal bipyramids that share corners with two equivalent Na(1)F8 hexagonal bipyramids, corners with two equivalent Al(1)F6 octahedra, edges with four equivalent Na(2)F8 hexagonal bipyramids, edges with two equivalent Al(1)F6 octahedra, and edges with four equivalent Zn(1)F6 octahedra. The corner-sharing octahedral tilt angles are 49°. Both Na(1)-F(2) bond lengths are 2.25 Å. Both Na(1)-F(3) bond lengths are 2.74 Å. All Na(1)-F(1) bond lengths are 2.59 Å. In the second Na site, Na(2) is bonded to four equivalent F(1) and four equivalent F(2) atoms to form distorted NaF8 hexagonal bipyramids that share edges with two equivalent Na(2)F8 hexagonal bipyramids, edges with four equivalent Na(1)F8 hexagonal bipyramids, edges with two equivalent Zn(1)F6 octahedra, and edges with four equivalent Al(1)F6 octahedra. All Na(2)-F(1) bond lengths are 2.79 Å. All Na(2)-F(2) bond lengths are 2.50 Å. Zn(1) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form ZnF6 octahedra that share corners with two equivalent Zn(1)F6 octahedra, corners with four equivalent Al(1)F6 octahedra, edges with two equivalent Na(2)F8 hexagonal bipyramids, and edges with four equivalent Na(1)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 38-54°. Both Zn(1)-F(3) bond lengths are 2.03 Å. All Zn(1)-F(1) bond lengths are 2.05 Å. Al(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form AlF6 octahedra that share corners with two equivalent Na(1)F8 hexagonal bipyramids, corners with four equivalent Zn(1)F6 octahedra, edges with two equivalent Na(1)F8 hexagonal bipyramids, and edges with four equivalent Na(2)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 38°. Both Al(1)-F(2) bond lengths are 1.86 Å. All Al(1)-F(1) bond lengths are 1.82 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Zn(1), and one Al(1) atom. In the second F site, F(2) is bonded to one Na(1), two equivalent Na(2), and one Al(1) atom to form a mixture of distorted edge and corner-sharing FNa3Al tetrahedra. In the third F site, F(3) is bonded in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Zn(1) atoms.