Ca3Mn2(IrO6)2 crystallizes in the triclinic P1 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(10), one O(11), one O(12), one O(2), one O(3), one O(4), one O(5), and one O(7) atom. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one O(12), one O(2), one O(3), one O(4), one O(5), one O(7), one O(8), and one O(9) atom. In the third Ca site, Ca(3) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(2), one O(3), one O(6), one O(8), and one O(9) atom. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(10), one O(12), one O(2), one O(4), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent Ir(1)O6 octahedra and corners with four equivalent Ir(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-33°. In the second Mn site, Mn(2) is bonded to one O(11), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form MnO6 octahedra that share corners with two equivalent Ir(2)O6 octahedra and corners with four equivalent Ir(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-33°. There are two inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to one O(1), one O(11), one O(12), one O(3), one O(5), and one O(8) atom to form IrO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-33°. In the second Ir site, Ir(2) is bonded to one O(10), one O(2), one O(4), one O(6), one O(7), and one O(9) atom to form IrO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra and corners with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-33°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Ca(3), one Mn(1), and one Ir(1) atom. In the second O site, O(2) is bonded to one Ca(1), one Ca(2), one Ca(3), one Mn(1), and one Ir(2) atom to form a mixture of distorted corner and edge-sharing OCa3MnIr trigonal bipyramids. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), one Mn(2), and one Ir(1) atom. In the fourth O site, O(4) is bonded to one Ca(1), one Ca(2), one Mn(1), and one Ir(2) atom to form distorted OCa2MnIr trigonal pyramids that share  a cornercorner with one O(12)Ca2MnIr tetrahedra, corners with three equivalent O(7)Ca2MnIr tetrahedra,  a cornercorner with one O(10)Ca2MnIr trigonal pyramid,  a cornercorner with one O(11)Ca2MnIr trigonal pyramid,  an edgeedge with one O(12)Ca2MnIr tetrahedra, edges with two equivalent O(2)Ca3MnIr trigonal bipyramids,  an edgeedge with one O(10)Ca2MnIr trigonal pyramid, and  an edgeedge with one O(5)Ca2MnIr trigonal pyramid. In the fifth O site, O(5) is bonded to one Ca(1), one Ca(2), one Mn(2), and one Ir(1) atom to form distorted OCa2MnIr trigonal pyramids that share  a cornercorner with one O(12)Ca2MnIr tetrahedra, corners with three equivalent O(7)Ca2MnIr tetrahedra, corners with two equivalent O(2)Ca3MnIr trigonal bipyramids,  a cornercorner with one O(10)Ca2MnIr trigonal pyramid,  a cornercorner with one O(11)Ca2MnIr trigonal pyramid,  an edgeedge with one O(12)Ca2MnIr tetrahedra,  an edgeedge with one O(11)Ca2MnIr trigonal pyramid, and  an edgeedge with one O(4)Ca2MnIr trigonal pyramid. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ca(3), one Mn(2), and one Ir(2) atom. In the seventh O site, O(7) is bonded to one Ca(1), one Ca(2), one Mn(2), and one Ir(2) atom to form distorted OCa2MnIr tetrahedra that share corners with two equivalent O(12)Ca2MnIr tetrahedra,  a cornercorner with one O(2)Ca3MnIr trigonal bipyramid, corners with three equivalent O(4)Ca2MnIr trigonal pyramids, corners with three equivalent O(5)Ca2MnIr trigonal pyramids,  an edgeedge with one O(2)Ca3MnIr trigonal bipyramid,  an edgeedge with one O(10)Ca2MnIr trigonal pyramid, and  an edgeedge with one O(11)Ca2MnIr trigonal pyramid. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Ca(2), one Ca(3), one Mn(2), and one Ir(1) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Ca(2), one Ca(3), one Mn(1), and one Ir(2) atom. In the tenth O site, O(10) is bonded to one Ca(1), one Ca(3), one Mn(1), and one Ir(2) atom to form distorted OCa2MnIr trigonal pyramids that share corners with two equivalent O(2)Ca3MnIr trigonal bipyramids,  a cornercorner with one O(4)Ca2MnIr trigonal pyramid,  a cornercorner with one O(5)Ca2MnIr trigonal pyramid, corners with two equivalent O(11)Ca2MnIr trigonal pyramids,  an edgeedge with one O(12)Ca2MnIr tetrahedra,  an edgeedge with one O(7)Ca2MnIr tetrahedra,  an edgeedge with one O(2)Ca3MnIr trigonal bipyramid, and  an edgeedge with one O(4)Ca2MnIr trigonal pyramid. In the eleventh O site, O(11) is bonded to one Ca(1), one Ca(3), one Mn(2), and one Ir(1) atom to form distorted OCa2MnIr trigonal pyramids that share corners with two equivalent O(2)Ca3MnIr trigonal bipyramids,  a cornercorner with one O(4)Ca2MnIr trigonal pyramid,  a cornercorner with one O(5)Ca2MnIr trigonal pyramid, corners with two equivalent O(10)Ca2MnIr trigonal pyramids,  an edgeedge with one O(12)Ca2MnIr tetrahedra,  an edgeedge with one O(7)Ca2MnIr tetrahedra, and  an edgeedge with one O(5)Ca2MnIr trigonal pyramid. In the twelfth O site, O(12) is bonded to one Ca(1), one Ca(2), one Mn(1), and one Ir(1) atom to form distorted OCa2MnIr tetrahedra that share corners with two equivalent O(7)Ca2MnIr tetrahedra, corners with three equivalent O(2)Ca3MnIr trigonal bipyramids,  a cornercorner with one O(4)Ca2MnIr trigonal pyramid,  a cornercorner with one O(5)Ca2MnIr trigonal pyramid,  an edgeedge with one O(10)Ca2MnIr trigonal pyramid,  an edgeedge with one O(11)Ca2MnIr trigonal pyramid,  an edgeedge with one O(4)Ca2MnIr trigonal pyramid, and  an edgeedge with one O(5)Ca2MnIr trigonal pyramid.
Ca3Mn2(IrO6)2 crystallizes in the triclinic P1 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(10), one O(11), one O(12), one O(2), one O(3), one O(4), one O(5), and one O(7) atom. The Ca(1)-O(10) bond length is 2.56 Å. The Ca(1)-O(11) bond length is 2.56 Å. The Ca(1)-O(12) bond length is 2.43 Å. The Ca(1)-O(2) bond length is 2.35 Å. The Ca(1)-O(3) bond length is 2.36 Å. The Ca(1)-O(4) bond length is 2.52 Å. The Ca(1)-O(5) bond length is 2.50 Å. The Ca(1)-O(7) bond length is 2.34 Å. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one O(12), one O(2), one O(3), one O(4), one O(5), one O(7), one O(8), and one O(9) atom. The Ca(2)-O(12) bond length is 2.31 Å. The Ca(2)-O(2) bond length is 2.55 Å. The Ca(2)-O(3) bond length is 2.55 Å. The Ca(2)-O(4) bond length is 2.35 Å. The Ca(2)-O(5) bond length is 2.35 Å. The Ca(2)-O(7) bond length is 2.39 Å. The Ca(2)-O(8) bond length is 2.72 Å. The Ca(2)-O(9) bond length is 2.72 Å. In the third Ca site, Ca(3) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(2), one O(3), one O(6), one O(8), and one O(9) atom. The Ca(3)-O(1) bond length is 2.43 Å. The Ca(3)-O(10) bond length is 2.33 Å. The Ca(3)-O(11) bond length is 2.33 Å. The Ca(3)-O(2) bond length is 2.66 Å. The Ca(3)-O(3) bond length is 2.67 Å. The Ca(3)-O(6) bond length is 2.32 Å. The Ca(3)-O(8) bond length is 2.56 Å. The Ca(3)-O(9) bond length is 2.57 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(10), one O(12), one O(2), one O(4), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent Ir(1)O6 octahedra and corners with four equivalent Ir(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-33°. The Mn(1)-O(1) bond length is 1.98 Å. The Mn(1)-O(10) bond length is 2.02 Å. The Mn(1)-O(12) bond length is 2.08 Å. The Mn(1)-O(2) bond length is 2.06 Å. The Mn(1)-O(4) bond length is 2.01 Å. The Mn(1)-O(9) bond length is 1.97 Å. In the second Mn site, Mn(2) is bonded to one O(11), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form MnO6 octahedra that share corners with two equivalent Ir(2)O6 octahedra and corners with four equivalent Ir(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-33°. The Mn(2)-O(11) bond length is 2.01 Å. The Mn(2)-O(3) bond length is 2.08 Å. The Mn(2)-O(5) bond length is 1.98 Å. The Mn(2)-O(6) bond length is 1.98 Å. The Mn(2)-O(7) bond length is 2.07 Å. The Mn(2)-O(8) bond length is 2.02 Å. There are two inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to one O(1), one O(11), one O(12), one O(3), one O(5), and one O(8) atom to form IrO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-33°. The Ir(1)-O(1) bond length is 1.90 Å. The Ir(1)-O(11) bond length is 1.96 Å. The Ir(1)-O(12) bond length is 2.00 Å. The Ir(1)-O(3) bond length is 1.98 Å. The Ir(1)-O(5) bond length is 1.97 Å. The Ir(1)-O(8) bond length is 1.93 Å. In the second Ir site, Ir(2) is bonded to one O(10), one O(2), one O(4), one O(6), one O(7), and one O(9) atom to form IrO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra and corners with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-33°. The Ir(2)-O(10) bond length is 1.95 Å. The Ir(2)-O(2) bond length is 1.99 Å. The Ir(2)-O(4) bond length is 1.96 Å. The Ir(2)-O(6) bond length is 1.91 Å. The Ir(2)-O(7) bond length is 2.00 Å. The Ir(2)-O(9) bond length is 1.96 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Ca(3), one Mn(1), and one Ir(1) atom. In the second O site, O(2) is bonded to one Ca(1), one Ca(2), one Ca(3), one Mn(1), and one Ir(2) atom to form a mixture of distorted corner and edge-sharing OCa3MnIr trigonal bipyramids. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), one Mn(2), and one Ir(1) atom. In the fourth O site, O(4) is bonded to one Ca(1), one Ca(2), one Mn(1), and one Ir(2) atom to form distorted OCa2MnIr trigonal pyramids that share  a cornercorner with one O(12)Ca2MnIr tetrahedra, corners with three equivalent O(7)Ca2MnIr tetrahedra,  a cornercorner with one O(10)Ca2MnIr trigonal pyramid,  a cornercorner with one O(11)Ca2MnIr trigonal pyramid,  an edgeedge with one O(12)Ca2MnIr tetrahedra, edges with two equivalent O(2)Ca3MnIr trigonal bipyramids,  an edgeedge with one O(10)Ca2MnIr trigonal pyramid, and  an edgeedge with one O(5)Ca2MnIr trigonal pyramid. In the fifth O site, O(5) is bonded to one Ca(1), one Ca(2), one Mn(2), and one Ir(1) atom to form distorted OCa2MnIr trigonal pyramids that share  a cornercorner with one O(12)Ca2MnIr tetrahedra, corners with three equivalent O(7)Ca2MnIr tetrahedra, corners with two equivalent O(2)Ca3MnIr trigonal bipyramids,  a cornercorner with one O(10)Ca2MnIr trigonal pyramid,  a cornercorner with one O(11)Ca2MnIr trigonal pyramid,  an edgeedge with one O(12)Ca2MnIr tetrahedra,  an edgeedge with one O(11)Ca2MnIr trigonal pyramid, and  an edgeedge with one O(4)Ca2MnIr trigonal pyramid. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ca(3), one Mn(2), and one Ir(2) atom. In the seventh O site, O(7) is bonded to one Ca(1), one Ca(2), one Mn(2), and one Ir(2) atom to form distorted OCa2MnIr tetrahedra that share corners with two equivalent O(12)Ca2MnIr tetrahedra,  a cornercorner with one O(2)Ca3MnIr trigonal bipyramid, corners with three equivalent O(4)Ca2MnIr trigonal pyramids, corners with three equivalent O(5)Ca2MnIr trigonal pyramids,  an edgeedge with one O(2)Ca3MnIr trigonal bipyramid,  an edgeedge with one O(10)Ca2MnIr trigonal pyramid, and  an edgeedge with one O(11)Ca2MnIr trigonal pyramid. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Ca(2), one Ca(3), one Mn(2), and one Ir(1) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Ca(2), one Ca(3), one Mn(1), and one Ir(2) atom. In the tenth O site, O(10) is bonded to one Ca(1), one Ca(3), one Mn(1), and one Ir(2) atom to form distorted OCa2MnIr trigonal pyramids that share corners with two equivalent O(2)Ca3MnIr trigonal bipyramids,  a cornercorner with one O(4)Ca2MnIr trigonal pyramid,  a cornercorner with one O(5)Ca2MnIr trigonal pyramid, corners with two equivalent O(11)Ca2MnIr trigonal pyramids,  an edgeedge with one O(12)Ca2MnIr tetrahedra,  an edgeedge with one O(7)Ca2MnIr tetrahedra,  an edgeedge with one O(2)Ca3MnIr trigonal bipyramid, and  an edgeedge with one O(4)Ca2MnIr trigonal pyramid. In the eleventh O site, O(11) is bonded to one Ca(1), one Ca(3), one Mn(2), and one Ir(1) atom to form distorted OCa2MnIr trigonal pyramids that share corners with two equivalent O(2)Ca3MnIr trigonal bipyramids,  a cornercorner with one O(4)Ca2MnIr trigonal pyramid,  a cornercorner with one O(5)Ca2MnIr trigonal pyramid, corners with two equivalent O(10)Ca2MnIr trigonal pyramids,  an edgeedge with one O(12)Ca2MnIr tetrahedra,  an edgeedge with one O(7)Ca2MnIr tetrahedra, and  an edgeedge with one O(5)Ca2MnIr trigonal pyramid. In the twelfth O site, O(12) is bonded to one Ca(1), one Ca(2), one Mn(1), and one Ir(1) atom to form distorted OCa2MnIr tetrahedra that share corners with two equivalent O(7)Ca2MnIr tetrahedra, corners with three equivalent O(2)Ca3MnIr trigonal bipyramids,  a cornercorner with one O(4)Ca2MnIr trigonal pyramid,  a cornercorner with one O(5)Ca2MnIr trigonal pyramid,  an edgeedge with one O(10)Ca2MnIr trigonal pyramid,  an edgeedge with one O(11)Ca2MnIr trigonal pyramid,  an edgeedge with one O(4)Ca2MnIr trigonal pyramid, and  an edgeedge with one O(5)Ca2MnIr trigonal pyramid.