Ca8TiMn7O22 crystallizes in the tetragonal P4mm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted q6 geometry to two equivalent O(2), two equivalent O(5), two equivalent O(6), two equivalent O(7), and two equivalent O(8) atoms. In the second Ca site, Ca(2) is bonded to one O(1), one O(4), two equivalent O(3), two equivalent O(5), two equivalent O(6), two equivalent O(7), and two equivalent O(8) atoms to form CaO12 cuboctahedra that share corners with four equivalent Ca(2)O12 cuboctahedra, faces with four equivalent Ca(2)O12 cuboctahedra, faces with two equivalent Mn(2)O6 octahedra, faces with two equivalent Mn(3)O6 octahedra,  a faceface with one Ti(1)O5 square pyramid,  a faceface with one Mn(1)O5 square pyramid,  a faceface with one Mn(4)O5 square pyramid, and  a faceface with one Mn(5)O5 square pyramid. Ti(1) is bonded to one O(1) and four equivalent O(5) atoms to form TiO5 square pyramids that share corners with four equivalent Mn(2)O6 octahedra,  a cornercorner with one Mn(1)O5 square pyramid, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 12°. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1) and four equivalent O(6) atoms to form MnO5 square pyramids that share corners with four equivalent Mn(3)O6 octahedra,  a cornercorner with one Ti(1)O5 square pyramid, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 6°. In the second Mn site, Mn(2) is bonded to one O(2), one O(3), two equivalent O(5), and two equivalent O(7) atoms to form MnO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra, corners with two equivalent Ti(1)O5 square pyramids, corners with two equivalent Mn(4)O5 square pyramids, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedra are not tilted. In the third Mn site, Mn(3) is bonded to one O(2), one O(3), two equivalent O(6), and two equivalent O(8) atoms to form MnO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(1)O5 square pyramids, corners with two equivalent Mn(5)O5 square pyramids, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedra are not tilted. In the fourth Mn site, Mn(4) is bonded to one O(4) and four equivalent O(7) atoms to form MnO5 square pyramids that share corners with four equivalent Mn(2)O6 octahedra,  a cornercorner with one Mn(5)O5 square pyramid, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 10°. In the fifth Mn site, Mn(5) is bonded to one O(4) and four equivalent O(8) atoms to form MnO5 square pyramids that share corners with four equivalent Mn(3)O6 octahedra,  a cornercorner with one Mn(4)O5 square pyramid, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 8°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to four equivalent Ca(2), one Ti(1), and one Mn(1) atom. In the second O site, O(2) is bonded in a linear geometry to four equivalent Ca(1), one Mn(2), and one Mn(3) atom. In the third O site, O(3) is bonded to four equivalent Ca(2), one Mn(2), and one Mn(3) atom to form a mixture of distorted face, corner, and edge-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 4-60°. In the fourth O site, O(4) is bonded to four equivalent Ca(2), one Mn(4), and one Mn(5) atom to form a mixture of distorted face, corner, and edge-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles are 58°. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one Ti(1), and one Mn(2) atom. In the sixth O site, O(6) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Mn(1), and one Mn(3) atom to form a mixture of distorted face, corner, and edge-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 5-60°. In the seventh O site, O(7) is bonded in a 6-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one Mn(2), and one Mn(4) atom. In the eighth O site, O(8) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Mn(3), and one Mn(5) atom to form a mixture of distorted face, corner, and edge-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 6-59°.
Ca8TiMn7O22 crystallizes in the tetragonal P4mm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted q6 geometry to two equivalent O(2), two equivalent O(5), two equivalent O(6), two equivalent O(7), and two equivalent O(8) atoms. Both Ca(1)-O(2) bond lengths are 2.72 Å. Both Ca(1)-O(5) bond lengths are 2.61 Å. Both Ca(1)-O(6) bond lengths are 2.62 Å. Both Ca(1)-O(7) bond lengths are 2.59 Å. Both Ca(1)-O(8) bond lengths are 2.58 Å. In the second Ca site, Ca(2) is bonded to one O(1), one O(4), two equivalent O(3), two equivalent O(5), two equivalent O(6), two equivalent O(7), and two equivalent O(8) atoms to form CaO12 cuboctahedra that share corners with four equivalent Ca(2)O12 cuboctahedra, faces with four equivalent Ca(2)O12 cuboctahedra, faces with two equivalent Mn(2)O6 octahedra, faces with two equivalent Mn(3)O6 octahedra,  a faceface with one Ti(1)O5 square pyramid,  a faceface with one Mn(1)O5 square pyramid,  a faceface with one Mn(4)O5 square pyramid, and  a faceface with one Mn(5)O5 square pyramid. The Ca(2)-O(1) bond length is 2.78 Å. The Ca(2)-O(4) bond length is 2.67 Å. Both Ca(2)-O(3) bond lengths are 2.72 Å. Both Ca(2)-O(5) bond lengths are 2.93 Å. Both Ca(2)-O(6) bond lengths are 2.79 Å. Both Ca(2)-O(7) bond lengths are 2.87 Å. Both Ca(2)-O(8) bond lengths are 2.75 Å. Ti(1) is bonded to one O(1) and four equivalent O(5) atoms to form TiO5 square pyramids that share corners with four equivalent Mn(2)O6 octahedra,  a cornercorner with one Mn(1)O5 square pyramid, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 12°. The Ti(1)-O(1) bond length is 1.77 Å. All Ti(1)-O(5) bond lengths are 1.92 Å. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1) and four equivalent O(6) atoms to form MnO5 square pyramids that share corners with four equivalent Mn(3)O6 octahedra,  a cornercorner with one Ti(1)O5 square pyramid, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 6°. The Mn(1)-O(1) bond length is 1.98 Å. All Mn(1)-O(6) bond lengths are 1.91 Å. In the second Mn site, Mn(2) is bonded to one O(2), one O(3), two equivalent O(5), and two equivalent O(7) atoms to form MnO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra, corners with two equivalent Ti(1)O5 square pyramids, corners with two equivalent Mn(4)O5 square pyramids, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedra are not tilted. The Mn(2)-O(2) bond length is 1.85 Å. The Mn(2)-O(3) bond length is 1.97 Å. Both Mn(2)-O(5) bond lengths are 1.96 Å. Both Mn(2)-O(7) bond lengths are 1.96 Å. In the third Mn site, Mn(3) is bonded to one O(2), one O(3), two equivalent O(6), and two equivalent O(8) atoms to form MnO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(1)O5 square pyramids, corners with two equivalent Mn(5)O5 square pyramids, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedra are not tilted. The Mn(3)-O(2) bond length is 1.85 Å. The Mn(3)-O(3) bond length is 1.98 Å. Both Mn(3)-O(6) bond lengths are 1.95 Å. Both Mn(3)-O(8) bond lengths are 1.96 Å. In the fourth Mn site, Mn(4) is bonded to one O(4) and four equivalent O(7) atoms to form MnO5 square pyramids that share corners with four equivalent Mn(2)O6 octahedra,  a cornercorner with one Mn(5)O5 square pyramid, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 10°. The Mn(4)-O(4) bond length is 1.88 Å. All Mn(4)-O(7) bond lengths are 1.90 Å. In the fifth Mn site, Mn(5) is bonded to one O(4) and four equivalent O(8) atoms to form MnO5 square pyramids that share corners with four equivalent Mn(3)O6 octahedra,  a cornercorner with one Mn(4)O5 square pyramid, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 8°. The Mn(5)-O(4) bond length is 1.89 Å. All Mn(5)-O(8) bond lengths are 1.90 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to four equivalent Ca(2), one Ti(1), and one Mn(1) atom. In the second O site, O(2) is bonded in a linear geometry to four equivalent Ca(1), one Mn(2), and one Mn(3) atom. In the third O site, O(3) is bonded to four equivalent Ca(2), one Mn(2), and one Mn(3) atom to form a mixture of distorted face, corner, and edge-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 4-60°. In the fourth O site, O(4) is bonded to four equivalent Ca(2), one Mn(4), and one Mn(5) atom to form a mixture of distorted face, corner, and edge-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles are 58°. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one Ti(1), and one Mn(2) atom. In the sixth O site, O(6) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Mn(1), and one Mn(3) atom to form a mixture of distorted face, corner, and edge-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 5-60°. In the seventh O site, O(7) is bonded in a 6-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one Mn(2), and one Mn(4) atom. In the eighth O site, O(8) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Mn(3), and one Mn(5) atom to form a mixture of distorted face, corner, and edge-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 6-59°.