Ca(CuO2)2 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. Ca(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form CaO6 octahedra that share corners with six equivalent Cu(1)O4 tetrahedra, edges with two equivalent Ca(1)O6 octahedra, and edges with four equivalent Cu(2)O6 octahedra. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form CuO4 tetrahedra that share corners with six equivalent Ca(1)O6 octahedra and corners with six equivalent Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-61°. In the second Cu site, Cu(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CuO6 octahedra that share corners with six equivalent Cu(1)O4 tetrahedra, edges with two equivalent Cu(2)O6 octahedra, and edges with four equivalent Ca(1)O6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Ca(1), one Cu(1), and one Cu(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Cu(1), and two equivalent Cu(2) atoms.
Ca(CuO2)2 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. Ca(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form CaO6 octahedra that share corners with six equivalent Cu(1)O4 tetrahedra, edges with two equivalent Ca(1)O6 octahedra, and edges with four equivalent Cu(2)O6 octahedra. Both Ca(1)-O(2) bond lengths are 2.29 Å. All Ca(1)-O(1) bond lengths are 2.25 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form CuO4 tetrahedra that share corners with six equivalent Ca(1)O6 octahedra and corners with six equivalent Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-61°. Both Cu(1)-O(1) bond lengths are 1.93 Å. Both Cu(1)-O(2) bond lengths are 1.92 Å. In the second Cu site, Cu(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CuO6 octahedra that share corners with six equivalent Cu(1)O4 tetrahedra, edges with two equivalent Cu(2)O6 octahedra, and edges with four equivalent Ca(1)O6 octahedra. Both Cu(2)-O(1) bond lengths are 1.86 Å. All Cu(2)-O(2) bond lengths are 2.19 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Ca(1), one Cu(1), and one Cu(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Cu(1), and two equivalent Cu(2) atoms.