Ca3CuMnO6 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to one O(3), one O(4), one O(5), one O(6), two equivalent O(1), and two equivalent O(2) atoms. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(4), one O(5), two equivalent O(3), and two equivalent O(6) atoms. In the third Ca site, Ca(3) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(3), one O(6), two equivalent O(4), and two equivalent O(5) atoms. Mn(1) is bonded in an octahedral geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. Cu(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(4), one O(5), and one O(6) atom. There are six inequivalent O sites. In the first O site, O(6) is bonded to one Ca(1), one Ca(3), two equivalent Ca(2), one Mn(1), and one Cu(1) atom to form a mixture of distorted corner, edge, and face-sharing OCa4MnCu octahedra. The corner-sharing octahedral tilt angles range from 5-60°. In the second O site, O(1) is bonded to one Ca(2), one Ca(3), two equivalent Ca(1), one Mn(1), and one Cu(1) atom to form a mixture of distorted corner, edge, and face-sharing OCa4MnCu octahedra. The corner-sharing octahedral tilt angles range from 22-67°. In the third O site, O(2) is bonded in a 5-coordinate geometry to one Ca(2), one Ca(3), two equivalent Ca(1), and one Mn(1) atom. In the fourth O site, O(3) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(3), two equivalent Ca(2), and one Mn(1) atom. In the fifth O site, O(4) is bonded to one Ca(1), one Ca(2), two equivalent Ca(3), one Mn(1), and one Cu(1) atom to form a mixture of distorted corner, edge, and face-sharing OCa4MnCu octahedra. The corner-sharing octahedral tilt angles range from 5-67°. In the sixth O site, O(5) is bonded to one Ca(1), one Ca(2), two equivalent Ca(3), one Mn(1), and one Cu(1) atom to form a mixture of distorted corner, edge, and face-sharing OCa4MnCu octahedra. The corner-sharing octahedral tilt angles range from 5-63°.
Ca3CuMnO6 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to one O(3), one O(4), one O(5), one O(6), two equivalent O(1), and two equivalent O(2) atoms. The Ca(1)-O(3) bond length is 2.33 Å. The Ca(1)-O(4) bond length is 2.59 Å. The Ca(1)-O(5) bond length is 2.73 Å. The Ca(1)-O(6) bond length is 2.58 Å. There is one shorter (2.59 Å) and one longer (2.65 Å) Ca(1)-O(1) bond length. There is one shorter (2.30 Å) and one longer (2.41 Å) Ca(1)-O(2) bond length. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(4), one O(5), two equivalent O(3), and two equivalent O(6) atoms. The Ca(2)-O(1) bond length is 2.38 Å. The Ca(2)-O(2) bond length is 2.36 Å. The Ca(2)-O(4) bond length is 2.64 Å. The Ca(2)-O(5) bond length is 2.54 Å. There is one shorter (2.52 Å) and one longer (2.62 Å) Ca(2)-O(3) bond length. There is one shorter (2.41 Å) and one longer (2.50 Å) Ca(2)-O(6) bond length. In the third Ca site, Ca(3) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(3), one O(6), two equivalent O(4), and two equivalent O(5) atoms. The Ca(3)-O(1) bond length is 2.46 Å. The Ca(3)-O(2) bond length is 2.64 Å. The Ca(3)-O(3) bond length is 2.36 Å. The Ca(3)-O(6) bond length is 2.64 Å. There is one shorter (2.39 Å) and one longer (2.57 Å) Ca(3)-O(4) bond length. There is one shorter (2.37 Å) and one longer (2.53 Å) Ca(3)-O(5) bond length. Mn(1) is bonded in an octahedral geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Mn(1)-O(1) bond length is 1.98 Å. The Mn(1)-O(2) bond length is 1.91 Å. The Mn(1)-O(3) bond length is 1.90 Å. The Mn(1)-O(4) bond length is 1.93 Å. The Mn(1)-O(5) bond length is 1.95 Å. The Mn(1)-O(6) bond length is 1.97 Å. Cu(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(4), one O(5), and one O(6) atom. The Cu(1)-O(1) bond length is 2.01 Å. The Cu(1)-O(4) bond length is 1.98 Å. The Cu(1)-O(5) bond length is 2.02 Å. The Cu(1)-O(6) bond length is 2.02 Å. There are six inequivalent O sites. In the first O site, O(6) is bonded to one Ca(1), one Ca(3), two equivalent Ca(2), one Mn(1), and one Cu(1) atom to form a mixture of distorted corner, edge, and face-sharing OCa4MnCu octahedra. The corner-sharing octahedral tilt angles range from 5-60°. In the second O site, O(1) is bonded to one Ca(2), one Ca(3), two equivalent Ca(1), one Mn(1), and one Cu(1) atom to form a mixture of distorted corner, edge, and face-sharing OCa4MnCu octahedra. The corner-sharing octahedral tilt angles range from 22-67°. In the third O site, O(2) is bonded in a 5-coordinate geometry to one Ca(2), one Ca(3), two equivalent Ca(1), and one Mn(1) atom. In the fourth O site, O(3) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(3), two equivalent Ca(2), and one Mn(1) atom. In the fifth O site, O(4) is bonded to one Ca(1), one Ca(2), two equivalent Ca(3), one Mn(1), and one Cu(1) atom to form a mixture of distorted corner, edge, and face-sharing OCa4MnCu octahedra. The corner-sharing octahedral tilt angles range from 5-67°. In the sixth O site, O(5) is bonded to one Ca(1), one Ca(2), two equivalent Ca(3), one Mn(1), and one Cu(1) atom to form a mixture of distorted corner, edge, and face-sharing OCa4MnCu octahedra. The corner-sharing octahedral tilt angles range from 5-63°.