Ca3CoO6 crystallizes in the triclinic P-1 space group. There are six inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to one O(10), one O(11), one O(3), one O(5), one O(7), one O(9), and two equivalent O(1) atoms. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one O(10), one O(12), one O(4), one O(6), one O(8), one O(9), and two equivalent O(2) atoms. In the third Ca site, Ca(3) is bonded in a 8-coordinate geometry to one O(1), one O(11), one O(12), one O(4), one O(5), one O(6), one O(7), and one O(9) atom. In the fourth Ca site, Ca(4) is bonded in a 8-coordinate geometry to one O(10), one O(11), one O(12), one O(2), one O(3), one O(5), one O(6), and one O(8) atom. In the fifth Ca site, Ca(5) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(5), one O(7), one O(8), and two equivalent O(3) atoms. In the sixth Ca site, Ca(6) is bonded in a 8-coordinate geometry to one O(12), one O(2), one O(6), one O(7), one O(8), one O(9), and two equivalent O(4) atoms. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded in an octahedral geometry to two equivalent O(10), two equivalent O(11), and two equivalent O(3) atoms. In the second Co site, Co(2) is bonded in an octahedral geometry to two equivalent O(2), two equivalent O(6), and two equivalent O(8) atoms. In the third Co site, Co(3) is bonded in an octahedral geometry to two equivalent O(12), two equivalent O(4), and two equivalent O(9) atoms. In the fourth Co site, Co(4) is bonded in an octahedral geometry to two equivalent O(1), two equivalent O(5), and two equivalent O(7) atoms. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Ca(3), one Ca(5), two equivalent Ca(1), and one Co(4) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the second O site, O(2) is bonded to one Ca(4), one Ca(6), two equivalent Ca(2), and one Co(2) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the third O site, O(3) is bonded to one Ca(1), one Ca(4), two equivalent Ca(5), and one Co(1) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the fourth O site, O(4) is bonded to one Ca(2), one Ca(3), two equivalent Ca(6), and one Co(3) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the fifth O site, O(5) is bonded to one Ca(1), one Ca(3), one Ca(4), one Ca(5), and one Co(4) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the sixth O site, O(6) is bonded to one Ca(2), one Ca(3), one Ca(4), one Ca(6), and one Co(2) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the seventh O site, O(7) is bonded to one Ca(1), one Ca(3), one Ca(5), one Ca(6), and one Co(4) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the eighth O site, O(8) is bonded to one Ca(2), one Ca(4), one Ca(5), one Ca(6), and one Co(2) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the ninth O site, O(9) is bonded to one Ca(1), one Ca(2), one Ca(3), one Ca(6), and one Co(3) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the tenth O site, O(10) is bonded to one Ca(1), one Ca(2), one Ca(4), one Ca(5), and one Co(1) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the eleventh O site, O(11) is bonded to one Ca(1), one Ca(3), one Ca(4), one Ca(5), and one Co(1) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the twelfth O site, O(12) is bonded to one Ca(2), one Ca(3), one Ca(4), one Ca(6), and one Co(3) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids.
Ca3CoO6 crystallizes in the triclinic P-1 space group. There are six inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to one O(10), one O(11), one O(3), one O(5), one O(7), one O(9), and two equivalent O(1) atoms. The Ca(1)-O(10) bond length is 2.47 Å. The Ca(1)-O(11) bond length is 2.43 Å. The Ca(1)-O(3) bond length is 2.57 Å. The Ca(1)-O(5) bond length is 2.51 Å. The Ca(1)-O(7) bond length is 2.47 Å. The Ca(1)-O(9) bond length is 2.36 Å. There is one shorter (2.36 Å) and one longer (2.42 Å) Ca(1)-O(1) bond length. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one O(10), one O(12), one O(4), one O(6), one O(8), one O(9), and two equivalent O(2) atoms. The Ca(2)-O(10) bond length is 2.36 Å. The Ca(2)-O(12) bond length is 2.43 Å. The Ca(2)-O(4) bond length is 2.58 Å. The Ca(2)-O(6) bond length is 2.50 Å. The Ca(2)-O(8) bond length is 2.48 Å. The Ca(2)-O(9) bond length is 2.47 Å. There is one shorter (2.35 Å) and one longer (2.42 Å) Ca(2)-O(2) bond length. In the third Ca site, Ca(3) is bonded in a 8-coordinate geometry to one O(1), one O(11), one O(12), one O(4), one O(5), one O(6), one O(7), and one O(9) atom. The Ca(3)-O(1) bond length is 2.40 Å. The Ca(3)-O(11) bond length is 2.45 Å. The Ca(3)-O(12) bond length is 2.38 Å. The Ca(3)-O(4) bond length is 2.40 Å. The Ca(3)-O(5) bond length is 2.38 Å. The Ca(3)-O(6) bond length is 2.46 Å. The Ca(3)-O(7) bond length is 2.55 Å. The Ca(3)-O(9) bond length is 2.54 Å. In the fourth Ca site, Ca(4) is bonded in a 8-coordinate geometry to one O(10), one O(11), one O(12), one O(2), one O(3), one O(5), one O(6), and one O(8) atom. The Ca(4)-O(10) bond length is 2.55 Å. The Ca(4)-O(11) bond length is 2.38 Å. The Ca(4)-O(12) bond length is 2.46 Å. The Ca(4)-O(2) bond length is 2.40 Å. The Ca(4)-O(3) bond length is 2.41 Å. The Ca(4)-O(5) bond length is 2.45 Å. The Ca(4)-O(6) bond length is 2.38 Å. The Ca(4)-O(8) bond length is 2.54 Å. In the fifth Ca site, Ca(5) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(5), one O(7), one O(8), and two equivalent O(3) atoms. The Ca(5)-O(1) bond length is 2.58 Å. The Ca(5)-O(10) bond length is 2.46 Å. The Ca(5)-O(11) bond length is 2.51 Å. The Ca(5)-O(5) bond length is 2.43 Å. The Ca(5)-O(7) bond length is 2.47 Å. The Ca(5)-O(8) bond length is 2.37 Å. There is one shorter (2.36 Å) and one longer (2.42 Å) Ca(5)-O(3) bond length. In the sixth Ca site, Ca(6) is bonded in a 8-coordinate geometry to one O(12), one O(2), one O(6), one O(7), one O(8), one O(9), and two equivalent O(4) atoms. The Ca(6)-O(12) bond length is 2.50 Å. The Ca(6)-O(2) bond length is 2.58 Å. The Ca(6)-O(6) bond length is 2.43 Å. The Ca(6)-O(7) bond length is 2.36 Å. The Ca(6)-O(8) bond length is 2.48 Å. The Ca(6)-O(9) bond length is 2.48 Å. There is one shorter (2.36 Å) and one longer (2.42 Å) Ca(6)-O(4) bond length. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded in an octahedral geometry to two equivalent O(10), two equivalent O(11), and two equivalent O(3) atoms. Both Co(1)-O(10) bond lengths are 1.91 Å. Both Co(1)-O(11) bond lengths are 1.84 Å. Both Co(1)-O(3) bond lengths are 1.87 Å. In the second Co site, Co(2) is bonded in an octahedral geometry to two equivalent O(2), two equivalent O(6), and two equivalent O(8) atoms. Both Co(2)-O(2) bond lengths are 1.87 Å. Both Co(2)-O(6) bond lengths are 1.84 Å. Both Co(2)-O(8) bond lengths are 1.91 Å. In the third Co site, Co(3) is bonded in an octahedral geometry to two equivalent O(12), two equivalent O(4), and two equivalent O(9) atoms. Both Co(3)-O(12) bond lengths are 1.84 Å. Both Co(3)-O(4) bond lengths are 1.87 Å. Both Co(3)-O(9) bond lengths are 1.91 Å. In the fourth Co site, Co(4) is bonded in an octahedral geometry to two equivalent O(1), two equivalent O(5), and two equivalent O(7) atoms. Both Co(4)-O(1) bond lengths are 1.87 Å. Both Co(4)-O(5) bond lengths are 1.84 Å. Both Co(4)-O(7) bond lengths are 1.91 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Ca(3), one Ca(5), two equivalent Ca(1), and one Co(4) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the second O site, O(2) is bonded to one Ca(4), one Ca(6), two equivalent Ca(2), and one Co(2) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the third O site, O(3) is bonded to one Ca(1), one Ca(4), two equivalent Ca(5), and one Co(1) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the fourth O site, O(4) is bonded to one Ca(2), one Ca(3), two equivalent Ca(6), and one Co(3) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the fifth O site, O(5) is bonded to one Ca(1), one Ca(3), one Ca(4), one Ca(5), and one Co(4) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the sixth O site, O(6) is bonded to one Ca(2), one Ca(3), one Ca(4), one Ca(6), and one Co(2) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the seventh O site, O(7) is bonded to one Ca(1), one Ca(3), one Ca(5), one Ca(6), and one Co(4) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the eighth O site, O(8) is bonded to one Ca(2), one Ca(4), one Ca(5), one Ca(6), and one Co(2) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the ninth O site, O(9) is bonded to one Ca(1), one Ca(2), one Ca(3), one Ca(6), and one Co(3) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the tenth O site, O(10) is bonded to one Ca(1), one Ca(2), one Ca(4), one Ca(5), and one Co(1) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the eleventh O site, O(11) is bonded to one Ca(1), one Ca(3), one Ca(4), one Ca(5), and one Co(1) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids. In the twelfth O site, O(12) is bonded to one Ca(2), one Ca(3), one Ca(4), one Ca(6), and one Co(3) atom to form a mixture of distorted corner, face, and edge-sharing OCa4Co square pyramids.