NaCdAlF6 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one F(2), one F(4), two equivalent F(3), and two equivalent F(5) atoms to form distorted NaF6 octahedra that share corners with two equivalent Cd(1)F7 hexagonal pyramids, corners with five equivalent Al(1)F6 octahedra, edges with two equivalent Cd(1)F7 hexagonal pyramids, and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 53-55°. Cd(1) is bonded to one F(4), one F(5), two equivalent F(1), and three equivalent F(2) atoms to form distorted CdF7 hexagonal pyramids that share corners with two equivalent Na(1)F6 octahedra, corners with two equivalent Al(1)F6 octahedra, edges with four equivalent Cd(1)F7 hexagonal pyramids,  an edgeedge with one Al(1)F6 octahedra, and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. Al(1) is bonded to one F(1), one F(3), one F(4), one F(5), and two equivalent F(6) atoms to form AlF6 octahedra that share corners with two equivalent Cd(1)F7 hexagonal pyramids, corners with two equivalent Al(1)F6 octahedra, corners with five equivalent Na(1)F6 octahedra, and  an edgeedge with one Cd(1)F7 hexagonal pyramid. The corner-sharing octahedral tilt angles range from 4-55°. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Cd(1) and one Al(1) atom. In the second F site, F(2) is bonded to one Na(1) and three equivalent Cd(1) atoms to form FNaCd3 tetrahedra that share  a cornercorner with one F(5)Na2AlCd tetrahedra, corners with two equivalent F(2)NaCd3 tetrahedra, edges with two equivalent F(5)Na2AlCd tetrahedra, and edges with two equivalent F(2)NaCd3 tetrahedra. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one Al(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Na(1), one Cd(1), and one Al(1) atom. In the fifth F site, F(5) is bonded to two equivalent Na(1), one Cd(1), and one Al(1) atom to form distorted FNa2AlCd tetrahedra that share  a cornercorner with one F(2)NaCd3 tetrahedra, corners with two equivalent F(5)Na2AlCd tetrahedra, and edges with two equivalent F(2)NaCd3 tetrahedra. In the sixth F site, F(6) is bonded in a linear geometry to two equivalent Al(1) atoms.
NaCdAlF6 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one F(2), one F(4), two equivalent F(3), and two equivalent F(5) atoms to form distorted NaF6 octahedra that share corners with two equivalent Cd(1)F7 hexagonal pyramids, corners with five equivalent Al(1)F6 octahedra, edges with two equivalent Cd(1)F7 hexagonal pyramids, and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 53-55°. The Na(1)-F(2) bond length is 2.37 Å. The Na(1)-F(4) bond length is 2.32 Å. Both Na(1)-F(3) bond lengths are 2.35 Å. Both Na(1)-F(5) bond lengths are 2.56 Å. Cd(1) is bonded to one F(4), one F(5), two equivalent F(1), and three equivalent F(2) atoms to form distorted CdF7 hexagonal pyramids that share corners with two equivalent Na(1)F6 octahedra, corners with two equivalent Al(1)F6 octahedra, edges with four equivalent Cd(1)F7 hexagonal pyramids,  an edgeedge with one Al(1)F6 octahedra, and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. The Cd(1)-F(4) bond length is 2.29 Å. The Cd(1)-F(5) bond length is 2.35 Å. Both Cd(1)-F(1) bond lengths are 2.35 Å. There is one shorter (2.29 Å) and two longer (2.32 Å) Cd(1)-F(2) bond lengths. Al(1) is bonded to one F(1), one F(3), one F(4), one F(5), and two equivalent F(6) atoms to form AlF6 octahedra that share corners with two equivalent Cd(1)F7 hexagonal pyramids, corners with two equivalent Al(1)F6 octahedra, corners with five equivalent Na(1)F6 octahedra, and  an edgeedge with one Cd(1)F7 hexagonal pyramid. The corner-sharing octahedral tilt angles range from 4-55°. The Al(1)-F(1) bond length is 1.84 Å. The Al(1)-F(3) bond length is 1.78 Å. The Al(1)-F(4) bond length is 1.83 Å. The Al(1)-F(5) bond length is 1.85 Å. Both Al(1)-F(6) bond lengths are 1.85 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Cd(1) and one Al(1) atom. In the second F site, F(2) is bonded to one Na(1) and three equivalent Cd(1) atoms to form FNaCd3 tetrahedra that share  a cornercorner with one F(5)Na2AlCd tetrahedra, corners with two equivalent F(2)NaCd3 tetrahedra, edges with two equivalent F(5)Na2AlCd tetrahedra, and edges with two equivalent F(2)NaCd3 tetrahedra. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one Al(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Na(1), one Cd(1), and one Al(1) atom. In the fifth F site, F(5) is bonded to two equivalent Na(1), one Cd(1), and one Al(1) atom to form distorted FNa2AlCd tetrahedra that share  a cornercorner with one F(2)NaCd3 tetrahedra, corners with two equivalent F(5)Na2AlCd tetrahedra, and edges with two equivalent F(2)NaCd3 tetrahedra. In the sixth F site, F(6) is bonded in a linear geometry to two equivalent Al(1) atoms.