Ca5MnO6 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Ca sites. In the first Ca site, 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 Ca(3)O6 octahedra, edges with two equivalent Ca(1)O6 octahedra, edges with two equivalent Ca(3)O6 octahedra, edges with four equivalent Ca(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. In the second Ca site, Ca(2) is bonded to one O(1), two equivalent O(2), and three equivalent O(3) atoms to form CaO6 octahedra that share corners with three equivalent Ca(3)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Ca(1)O6 octahedra, edges with four equivalent Ca(2)O6 octahedra, and edges with five equivalent Ca(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the third Ca site, Ca(3) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form CaO6 octahedra that share corners with three equivalent Ca(1)O6 octahedra, corners with three equivalent Ca(2)O6 octahedra,  an edgeedge with one Ca(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Ca(3)O6 octahedra, and edges with five equivalent Ca(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. Mn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Ca(2)O6 octahedra, edges with two equivalent Ca(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Ca(1)O6 octahedra, and edges with four equivalent Ca(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Ca(2), two equivalent Ca(1), two equivalent Ca(3), and one Mn(1) atom to form OCa5Mn octahedra that share corners with three equivalent O(1)Ca5Mn octahedra, corners with three equivalent O(3)Ca6 octahedra, edges with three equivalent O(1)Ca5Mn octahedra, edges with three equivalent O(3)Ca6 octahedra, and edges with six equivalent O(2)Ca4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second O site, O(2) is bonded to one Ca(1), one Ca(3), two equivalent Ca(2), and two equivalent Mn(1) atoms to form OCa4Mn2 octahedra that share corners with three equivalent O(2)Ca4Mn2 octahedra, corners with three equivalent O(3)Ca6 octahedra, edges with three equivalent O(2)Ca4Mn2 octahedra, edges with three equivalent O(3)Ca6 octahedra, and edges with six equivalent O(1)Ca5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to three equivalent Ca(2) and three equivalent Ca(3) atoms to form OCa6 octahedra that share corners with three equivalent O(2)Ca4Mn2 octahedra, corners with three equivalent O(1)Ca5Mn octahedra, edges with three equivalent O(2)Ca4Mn2 octahedra, edges with three equivalent O(1)Ca5Mn octahedra, and edges with six equivalent O(3)Ca6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°.
Ca5MnO6 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Ca sites. In the first Ca site, 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 Ca(3)O6 octahedra, edges with two equivalent Ca(1)O6 octahedra, edges with two equivalent Ca(3)O6 octahedra, edges with four equivalent Ca(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. Both Ca(1)-O(2) bond lengths are 2.38 Å. All Ca(1)-O(1) bond lengths are 2.39 Å. In the second Ca site, Ca(2) is bonded to one O(1), two equivalent O(2), and three equivalent O(3) atoms to form CaO6 octahedra that share corners with three equivalent Ca(3)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Ca(1)O6 octahedra, edges with four equivalent Ca(2)O6 octahedra, and edges with five equivalent Ca(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. The Ca(2)-O(1) bond length is 2.42 Å. Both Ca(2)-O(2) bond lengths are 2.42 Å. All Ca(2)-O(3) bond lengths are 2.39 Å. In the third Ca site, Ca(3) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form CaO6 octahedra that share corners with three equivalent Ca(1)O6 octahedra, corners with three equivalent Ca(2)O6 octahedra,  an edgeedge with one Ca(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Ca(3)O6 octahedra, and edges with five equivalent Ca(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. The Ca(3)-O(2) bond length is 2.37 Å. Both Ca(3)-O(1) bond lengths are 2.37 Å. All Ca(3)-O(3) bond lengths are 2.42 Å. Mn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Ca(2)O6 octahedra, edges with two equivalent Ca(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Ca(1)O6 octahedra, and edges with four equivalent Ca(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. Both Mn(1)-O(1) bond lengths are 2.35 Å. All Mn(1)-O(2) bond lengths are 2.34 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Ca(2), two equivalent Ca(1), two equivalent Ca(3), and one Mn(1) atom to form OCa5Mn octahedra that share corners with three equivalent O(1)Ca5Mn octahedra, corners with three equivalent O(3)Ca6 octahedra, edges with three equivalent O(1)Ca5Mn octahedra, edges with three equivalent O(3)Ca6 octahedra, and edges with six equivalent O(2)Ca4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second O site, O(2) is bonded to one Ca(1), one Ca(3), two equivalent Ca(2), and two equivalent Mn(1) atoms to form OCa4Mn2 octahedra that share corners with three equivalent O(2)Ca4Mn2 octahedra, corners with three equivalent O(3)Ca6 octahedra, edges with three equivalent O(2)Ca4Mn2 octahedra, edges with three equivalent O(3)Ca6 octahedra, and edges with six equivalent O(1)Ca5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to three equivalent Ca(2) and three equivalent Ca(3) atoms to form OCa6 octahedra that share corners with three equivalent O(2)Ca4Mn2 octahedra, corners with three equivalent O(1)Ca5Mn octahedra, edges with three equivalent O(2)Ca4Mn2 octahedra, edges with three equivalent O(1)Ca5Mn octahedra, and edges with six equivalent O(3)Ca6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°.