CaCo4(CuO4)3 crystallizes in the triclinic P-1 space group. Ca(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), two equivalent O(5), and two equivalent O(6) atoms to form CaO12 cuboctahedra that share faces with two equivalent Co(1)O6 octahedra, faces with two equivalent Co(2)O6 octahedra, faces with two equivalent Co(3)O6 octahedra, and faces with two equivalent Co(4)O6 octahedra. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form CoO6 octahedra that share corners with two equivalent Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, corners with two equivalent Co(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 43-44°. In the second Co site, Co(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form CoO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, corners with two equivalent Co(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 43-44°. In the third Co site, Co(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form CoO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, corners with two equivalent Co(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 44°. In the fourth Co site, Co(4) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form CoO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 43-44°. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to two equivalent O(3) and two equivalent O(6) atoms. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. In the third Cu site, Cu(3) is bonded in a square co-planar geometry to two equivalent O(4) and two equivalent O(5) atoms. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Ca(1), one Co(2), one Co(4), and one Cu(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one Co(1), one Co(3), and one Cu(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one Co(2), one Co(3), and one Cu(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ca(1), one Co(3), one Co(4), and one Cu(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Ca(1), one Co(1), one Co(2), and one Cu(3) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ca(1), one Co(1), one Co(4), and one Cu(1) atom.
CaCo4(CuO4)3 crystallizes in the triclinic P-1 space group. Ca(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), two equivalent O(5), and two equivalent O(6) atoms to form CaO12 cuboctahedra that share faces with two equivalent Co(1)O6 octahedra, faces with two equivalent Co(2)O6 octahedra, faces with two equivalent Co(3)O6 octahedra, and faces with two equivalent Co(4)O6 octahedra. Both Ca(1)-O(1) bond lengths are 2.58 Å. Both Ca(1)-O(2) bond lengths are 2.61 Å. Both Ca(1)-O(3) bond lengths are 2.61 Å. Both Ca(1)-O(4) bond lengths are 2.58 Å. Both Ca(1)-O(5) bond lengths are 2.62 Å. Both Ca(1)-O(6) bond lengths are 2.60 Å. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form CoO6 octahedra that share corners with two equivalent Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, corners with two equivalent Co(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 43-44°. Both Co(1)-O(2) bond lengths are 1.96 Å. Both Co(1)-O(5) bond lengths are 2.02 Å. Both Co(1)-O(6) bond lengths are 1.94 Å. In the second Co site, Co(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form CoO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, corners with two equivalent Co(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 43-44°. Both Co(2)-O(1) bond lengths are 1.97 Å. Both Co(2)-O(3) bond lengths are 1.99 Å. Both Co(2)-O(5) bond lengths are 1.92 Å. In the third Co site, Co(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form CoO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, corners with two equivalent Co(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 44°. Both Co(3)-O(2) bond lengths are 2.00 Å. Both Co(3)-O(3) bond lengths are 1.96 Å. Both Co(3)-O(4) bond lengths are 1.97 Å. In the fourth Co site, Co(4) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form CoO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 43-44°. Both Co(4)-O(1) bond lengths are 1.98 Å. Both Co(4)-O(4) bond lengths are 1.98 Å. Both Co(4)-O(6) bond lengths are 2.01 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to two equivalent O(3) and two equivalent O(6) atoms. Both Cu(1)-O(3) bond lengths are 1.87 Å. Both Cu(1)-O(6) bond lengths are 1.87 Å. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Cu(2)-O(1) bond lengths are 1.88 Å. Both Cu(2)-O(2) bond lengths are 1.87 Å. In the third Cu site, Cu(3) is bonded in a square co-planar geometry to two equivalent O(4) and two equivalent O(5) atoms. Both Cu(3)-O(4) bond lengths are 1.88 Å. Both Cu(3)-O(5) bond lengths are 1.87 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Ca(1), one Co(2), one Co(4), and one Cu(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one Co(1), one Co(3), and one Cu(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one Co(2), one Co(3), and one Cu(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ca(1), one Co(3), one Co(4), and one Cu(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Ca(1), one Co(1), one Co(2), and one Cu(3) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ca(1), one Co(1), one Co(4), and one Cu(1) atom.