CsCuAlF6 crystallizes in the orthorhombic Pnma space group. Cs(1) is bonded in a 5-coordinate geometry to one F(1), two equivalent F(3), and two equivalent F(4) atoms. Cu(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra and corners with four equivalent Al(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-46°. Al(1) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form AlF6 octahedra that share corners with two equivalent Al(1)F6 octahedra and corners with four equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 29-45°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to one Cs(1) and two equivalent Cu(1) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Al(1) atoms. In the third F site, F(3) is bonded in a 2-coordinate geometry to one Cs(1), one Cu(1), and one Al(1) atom. In the fourth F site, F(4) is bonded in a 2-coordinate geometry to one Cs(1), one Cu(1), and one Al(1) atom.
CsCuAlF6 crystallizes in the orthorhombic Pnma space group. Cs(1) is bonded in a 5-coordinate geometry to one F(1), two equivalent F(3), and two equivalent F(4) atoms. The Cs(1)-F(1) bond length is 3.15 Å. Both Cs(1)-F(3) bond lengths are 3.11 Å. Both Cs(1)-F(4) bond lengths are 3.12 Å. Cu(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra and corners with four equivalent Al(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-46°. Both Cu(1)-F(1) bond lengths are 1.96 Å. Both Cu(1)-F(3) bond lengths are 2.09 Å. Both Cu(1)-F(4) bond lengths are 2.12 Å. Al(1) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form AlF6 octahedra that share corners with two equivalent Al(1)F6 octahedra and corners with four equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 29-45°. Both Al(1)-F(2) bond lengths are 1.86 Å. Both Al(1)-F(3) bond lengths are 1.81 Å. Both Al(1)-F(4) bond lengths are 1.82 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to one Cs(1) and two equivalent Cu(1) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Al(1) atoms. In the third F site, F(3) is bonded in a 2-coordinate geometry to one Cs(1), one Cu(1), and one Al(1) atom. In the fourth F site, F(4) is bonded in a 2-coordinate geometry to one Cs(1), one Cu(1), and one Al(1) atom.