Al5(CuO4)3 crystallizes in the monoclinic C2/m space group. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(4), one O(9), and two equivalent O(3) atoms to form CuO4 tetrahedra that share corners with three equivalent Al(1)O6 octahedra and corners with six equivalent Al(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-61°. In the second Cu site, Cu(2) is bonded to one O(5), one O(7), and two equivalent O(2) atoms to form CuO4 tetrahedra that share  a cornercorner with one Al(1)O6 octahedra, corners with two equivalent Al(3)O6 octahedra, corners with three equivalent Al(2)O6 octahedra, and corners with four equivalent Al(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-60°. In the third Cu site, Cu(3) is bonded to one O(6), one O(8), and two equivalent O(1) atoms to form CuO4 tetrahedra that share corners with two equivalent Al(1)O6 octahedra, corners with two equivalent Al(4)O6 octahedra, corners with three equivalent Al(2)O6 octahedra, and corners with four equivalent Al(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-62°. There are four inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(7), one O(9), two equivalent O(1), and two equivalent O(3) atoms to form AlO6 octahedra that share  a cornercorner with one Cu(2)O4 tetrahedra, corners with two equivalent Cu(3)O4 tetrahedra, corners with three equivalent Cu(1)O4 tetrahedra,  an edgeedge with one Al(2)O6 octahedra, and edges with four equivalent Al(3)O6 octahedra. In the second Al site, Al(2) is bonded to one O(5), one O(6), two equivalent O(1), and two equivalent O(2) atoms to form AlO6 octahedra that share corners with three equivalent Cu(2)O4 tetrahedra, corners with three equivalent Cu(3)O4 tetrahedra,  an edgeedge with one Al(1)O6 octahedra, edges with two equivalent Al(3)O6 octahedra, and edges with two equivalent Al(4)O6 octahedra. In the third Al site, Al(3) is bonded to one O(1), one O(3), one O(4), one O(6), one O(7), and one O(9) atom to form AlO6 octahedra that share  a cornercorner with one Cu(2)O4 tetrahedra, corners with two equivalent Cu(3)O4 tetrahedra, corners with three equivalent Cu(1)O4 tetrahedra,  an edgeedge with one Al(2)O6 octahedra, edges with two equivalent Al(1)O6 octahedra, and edges with two equivalent Al(3)O6 octahedra. In the fourth Al site, Al(4) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(8) atoms to form AlO6 octahedra that share corners with two equivalent Cu(3)O4 tetrahedra, corners with four equivalent Cu(2)O4 tetrahedra, edges with two equivalent Al(2)O6 octahedra, and edges with two equivalent Al(4)O6 octahedra. There are nine inequivalent O sites. In the first O site, O(1) is bonded to one Cu(3), one Al(1), one Al(2), and one Al(3) atom to form a mixture of distorted corner and edge-sharing OAl3Cu tetrahedra. In the second O site, O(2) is bonded in a trigonal planar geometry to one Cu(2), one Al(2), and one Al(4) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Cu(1), one Al(1), and one Al(3) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Cu(1) and two equivalent Al(3) atoms. In the fifth O site, O(5) is bonded to one Cu(2), one Al(2), and two equivalent Al(4) atoms to form distorted corner-sharing OAl3Cu trigonal pyramids. In the sixth O site, O(6) is bonded to one Cu(3), one Al(2), and two equivalent Al(3) atoms to form a mixture of distorted corner and edge-sharing OAl3Cu tetrahedra. In the seventh O site, O(7) is bonded to one Cu(2), one Al(1), and two equivalent Al(3) atoms to form distorted corner-sharing OAl3Cu trigonal pyramids. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Cu(3) and two equivalent Al(4) atoms. In the ninth O site, O(9) is bonded to one Cu(1), one Al(1), and two equivalent Al(3) atoms to form a mixture of distorted corner and edge-sharing OAl3Cu tetrahedra.
Al5(CuO4)3 crystallizes in the monoclinic C2/m space group. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(4), one O(9), and two equivalent O(3) atoms to form CuO4 tetrahedra that share corners with three equivalent Al(1)O6 octahedra and corners with six equivalent Al(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-61°. The Cu(1)-O(4) bond length is 1.91 Å. The Cu(1)-O(9) bond length is 1.96 Å. Both Cu(1)-O(3) bond lengths are 1.91 Å. In the second Cu site, Cu(2) is bonded to one O(5), one O(7), and two equivalent O(2) atoms to form CuO4 tetrahedra that share  a cornercorner with one Al(1)O6 octahedra, corners with two equivalent Al(3)O6 octahedra, corners with three equivalent Al(2)O6 octahedra, and corners with four equivalent Al(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-60°. The Cu(2)-O(5) bond length is 1.95 Å. The Cu(2)-O(7) bond length is 2.03 Å. Both Cu(2)-O(2) bond lengths are 1.89 Å. In the third Cu site, Cu(3) is bonded to one O(6), one O(8), and two equivalent O(1) atoms to form CuO4 tetrahedra that share corners with two equivalent Al(1)O6 octahedra, corners with two equivalent Al(4)O6 octahedra, corners with three equivalent Al(2)O6 octahedra, and corners with four equivalent Al(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-62°. The Cu(3)-O(6) bond length is 1.98 Å. The Cu(3)-O(8) bond length is 1.89 Å. Both Cu(3)-O(1) bond lengths are 2.00 Å. There are four inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(7), one O(9), two equivalent O(1), and two equivalent O(3) atoms to form AlO6 octahedra that share  a cornercorner with one Cu(2)O4 tetrahedra, corners with two equivalent Cu(3)O4 tetrahedra, corners with three equivalent Cu(1)O4 tetrahedra,  an edgeedge with one Al(2)O6 octahedra, and edges with four equivalent Al(3)O6 octahedra. The Al(1)-O(7) bond length is 1.95 Å. The Al(1)-O(9) bond length is 1.95 Å. Both Al(1)-O(1) bond lengths are 1.95 Å. Both Al(1)-O(3) bond lengths are 1.88 Å. In the second Al site, Al(2) is bonded to one O(5), one O(6), two equivalent O(1), and two equivalent O(2) atoms to form AlO6 octahedra that share corners with three equivalent Cu(2)O4 tetrahedra, corners with three equivalent Cu(3)O4 tetrahedra,  an edgeedge with one Al(1)O6 octahedra, edges with two equivalent Al(3)O6 octahedra, and edges with two equivalent Al(4)O6 octahedra. The Al(2)-O(5) bond length is 1.96 Å. The Al(2)-O(6) bond length is 1.91 Å. Both Al(2)-O(1) bond lengths are 1.95 Å. Both Al(2)-O(2) bond lengths are 1.89 Å. In the third Al site, Al(3) is bonded to one O(1), one O(3), one O(4), one O(6), one O(7), and one O(9) atom to form AlO6 octahedra that share  a cornercorner with one Cu(2)O4 tetrahedra, corners with two equivalent Cu(3)O4 tetrahedra, corners with three equivalent Cu(1)O4 tetrahedra,  an edgeedge with one Al(2)O6 octahedra, edges with two equivalent Al(1)O6 octahedra, and edges with two equivalent Al(3)O6 octahedra. The Al(3)-O(1) bond length is 1.96 Å. The Al(3)-O(3) bond length is 1.88 Å. The Al(3)-O(4) bond length is 1.88 Å. The Al(3)-O(6) bond length is 1.96 Å. The Al(3)-O(7) bond length is 1.95 Å. The Al(3)-O(9) bond length is 1.94 Å. In the fourth Al site, Al(4) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(8) atoms to form AlO6 octahedra that share corners with two equivalent Cu(3)O4 tetrahedra, corners with four equivalent Cu(2)O4 tetrahedra, edges with two equivalent Al(2)O6 octahedra, and edges with two equivalent Al(4)O6 octahedra. Both Al(4)-O(2) bond lengths are 1.90 Å. Both Al(4)-O(5) bond lengths are 1.95 Å. Both Al(4)-O(8) bond lengths are 1.91 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded to one Cu(3), one Al(1), one Al(2), and one Al(3) atom to form a mixture of distorted corner and edge-sharing OAl3Cu tetrahedra. In the second O site, O(2) is bonded in a trigonal planar geometry to one Cu(2), one Al(2), and one Al(4) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Cu(1), one Al(1), and one Al(3) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Cu(1) and two equivalent Al(3) atoms. In the fifth O site, O(5) is bonded to one Cu(2), one Al(2), and two equivalent Al(4) atoms to form distorted corner-sharing OAl3Cu trigonal pyramids. In the sixth O site, O(6) is bonded to one Cu(3), one Al(2), and two equivalent Al(3) atoms to form a mixture of distorted corner and edge-sharing OAl3Cu tetrahedra. In the seventh O site, O(7) is bonded to one Cu(2), one Al(1), and two equivalent Al(3) atoms to form distorted corner-sharing OAl3Cu trigonal pyramids. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Cu(3) and two equivalent Al(4) atoms. In the ninth O site, O(9) is bonded to one Cu(1), one Al(1), and two equivalent Al(3) atoms to form a mixture of distorted corner and edge-sharing OAl3Cu tetrahedra.