CuAlO4F crystallizes in the monoclinic C2/m space group. Cu(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(4) atoms to form CuO5 square pyramids that share  a cornercorner with one Al(1)O2F4 octahedra, corners with two equivalent Al(2)O6 octahedra, and edges with two equivalent Cu(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 48-59°. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form AlO2F4 octahedra that share corners with two equivalent Cu(1)O5 square pyramids and edges with two equivalent Al(1)O2F4 octahedra. In the second Al site, Al(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form AlO6 octahedra that share corners with four equivalent Cu(1)O5 square pyramids and edges with two equivalent Al(2)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Cu(1) and one Al(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to two equivalent Cu(1) and one Al(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Al(2) and one O(4) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Cu(1) and one O(3) atom. F(1) is bonded in a water-like geometry to two equivalent Al(1) atoms.
CuAlO4F crystallizes in the monoclinic C2/m space group. Cu(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(4) atoms to form CuO5 square pyramids that share  a cornercorner with one Al(1)O2F4 octahedra, corners with two equivalent Al(2)O6 octahedra, and edges with two equivalent Cu(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 48-59°. The Cu(1)-O(1) bond length is 1.90 Å. Both Cu(1)-O(2) bond lengths are 1.89 Å. Both Cu(1)-O(4) bond lengths are 2.03 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form AlO2F4 octahedra that share corners with two equivalent Cu(1)O5 square pyramids and edges with two equivalent Al(1)O2F4 octahedra. Both Al(1)-O(1) bond lengths are 1.88 Å. All Al(1)-F(1) bond lengths are 1.87 Å. In the second Al site, Al(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form AlO6 octahedra that share corners with four equivalent Cu(1)O5 square pyramids and edges with two equivalent Al(2)O6 octahedra. Both Al(2)-O(2) bond lengths are 1.84 Å. All Al(2)-O(3) bond lengths are 1.94 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Cu(1) and one Al(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to two equivalent Cu(1) and one Al(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Al(2) and one O(4) atom. The O(3)-O(4) bond length is 1.44 Å. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Cu(1) and one O(3) atom. F(1) is bonded in a water-like geometry to two equivalent Al(1) atoms.