Cu2O3Cl crystallizes in the trigonal R-3 space group. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to six equivalent O(4) atoms to form distorted edge-sharing CuO6 octahedra. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted edge-sharing CuO6 octahedra. In the third Cu site, Cu(3) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent Cl(2) atoms to form distorted CuCl2O4 octahedra that share edges with two equivalent Cu(3)Cl2O4 octahedra, edges with two equivalent Cu(4)Cl2O4 octahedra, and edges with two equivalent Cu(2)O6 octahedra. In the fourth Cu site, Cu(4) is bonded to one O(1), one O(3), two equivalent O(4), one Cl(1), and one Cl(2) atom to form distorted CuCl2O4 octahedra that share  an edgeedge with one Cu(1)O6 octahedra,  an edgeedge with one Cu(2)O6 octahedra, edges with two equivalent Cu(3)Cl2O4 octahedra, and edges with two equivalent Cu(4)Cl2O4 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Cu(2), one Cu(3), and one Cu(4) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Cu(2) and two equivalent Cu(3) atoms. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Cu(2), one Cu(3), and one Cu(4) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Cu(1) and two equivalent Cu(4) atoms. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 3-coordinate geometry to three equivalent Cu(4) atoms. In the second Cl site, Cl(2) is bonded in a 3-coordinate geometry to one Cu(4) and two equivalent Cu(3) atoms.
Cu2O3Cl crystallizes in the trigonal R-3 space group. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to six equivalent O(4) atoms to form distorted edge-sharing CuO6 octahedra. All Cu(1)-O(4) bond lengths are 1.97 Å. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted edge-sharing CuO6 octahedra. Both Cu(2)-O(1) bond lengths are 1.91 Å. Both Cu(2)-O(2) bond lengths are 1.99 Å. Both Cu(2)-O(3) bond lengths are 2.04 Å. In the third Cu site, Cu(3) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent Cl(2) atoms to form distorted CuCl2O4 octahedra that share edges with two equivalent Cu(3)Cl2O4 octahedra, edges with two equivalent Cu(4)Cl2O4 octahedra, and edges with two equivalent Cu(2)O6 octahedra. The Cu(3)-O(1) bond length is 1.90 Å. The Cu(3)-O(3) bond length is 1.87 Å. There is one shorter (1.88 Å) and one longer (1.89 Å) Cu(3)-O(2) bond length. There is one shorter (2.65 Å) and one longer (2.66 Å) Cu(3)-Cl(2) bond length. In the fourth Cu site, Cu(4) is bonded to one O(1), one O(3), two equivalent O(4), one Cl(1), and one Cl(2) atom to form distorted CuCl2O4 octahedra that share  an edgeedge with one Cu(1)O6 octahedra,  an edgeedge with one Cu(2)O6 octahedra, edges with two equivalent Cu(3)Cl2O4 octahedra, and edges with two equivalent Cu(4)Cl2O4 octahedra. The Cu(4)-O(1) bond length is 1.90 Å. The Cu(4)-O(3) bond length is 1.88 Å. Both Cu(4)-O(4) bond lengths are 1.89 Å. The Cu(4)-Cl(1) bond length is 2.63 Å. The Cu(4)-Cl(2) bond length is 2.63 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Cu(2), one Cu(3), and one Cu(4) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Cu(2) and two equivalent Cu(3) atoms. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Cu(2), one Cu(3), and one Cu(4) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Cu(1) and two equivalent Cu(4) atoms. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 3-coordinate geometry to three equivalent Cu(4) atoms. In the second Cl site, Cl(2) is bonded in a 3-coordinate geometry to one Cu(4) and two equivalent Cu(3) atoms.