Ca4TiMn3O11 crystallizes in the orthorhombic Pmm2 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 10-coordinate geometry to one O(10), one O(11), one O(12), one O(13), one O(14), one O(2), one O(4), one O(7), one O(8), and one O(9) atom. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(12), one O(14), one O(3), one O(5), one O(6), and one O(8) atom. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), two equivalent O(11), and two equivalent O(7) atoms to form TiO5 trigonal bipyramids that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, and  a cornercorner with one Mn(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 13-19°. In the second Ti site, Ti(2) is bonded to one O(4), one O(5), two equivalent O(13), and two equivalent O(7) atoms to form TiO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, corners with two equivalent Mn(5)O5 square pyramids, and corners with two equivalent Ti(1)O5 trigonal bipyramids. The corner-sharing octahedra are not tilted. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), two equivalent O(12), and two equivalent O(8) atoms to form MnO5 square pyramids that share corners with two equivalent Mn(3)O6 octahedra, corners with two equivalent Mn(4)O6 octahedra, and  a cornercorner with one Ti(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 3-4°. In the second Mn site, Mn(2) is bonded to one O(2), one O(3), two equivalent O(11), and two equivalent O(9) atoms to form MnO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra, corners with two equivalent Mn(5)O5 square pyramids, and corners with two equivalent Ti(1)O5 trigonal bipyramids. 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(10), and two equivalent O(12) atoms to form MnO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(1)O5 square pyramids, and corners with two equivalent Mn(6)O5 square pyramids. The corner-sharing octahedra are not tilted. In the fourth Mn site, Mn(4) is bonded to one O(4), one O(5), two equivalent O(14), and two equivalent O(8) atoms to form MnO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Mn(1)O5 square pyramids, and corners with two equivalent Mn(6)O5 square pyramids. The corner-sharing octahedra are not tilted. In the fifth Mn site, Mn(5) is bonded to one O(6), two equivalent O(13), and two equivalent O(9) atoms to form MnO5 square pyramids that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, and  a cornercorner with one Mn(6)O5 square pyramid. The corner-sharing octahedral tilt angles range from 9-13°. In the sixth Mn site, Mn(6) is bonded to one O(6), two equivalent O(10), and two equivalent O(14) atoms to form MnO5 square pyramids that share corners with two equivalent Mn(3)O6 octahedra, corners with two equivalent Mn(4)O6 octahedra, and  a cornercorner with one Mn(5)O5 square pyramid. The corner-sharing octahedral tilt angles range from 3-8°. There are fourteen 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 distorted 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 and corner-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 53-55°. In the fourth O site, O(4) is bonded in a linear geometry to four equivalent Ca(1), one Ti(2), and one Mn(4) atom. In the fifth O site, O(5) is bonded in a distorted linear geometry to four equivalent Ca(2), one Ti(2), and one Mn(4) atom. In the sixth O site, O(6) is bonded in a distorted linear geometry to four equivalent Ca(2), one Mn(5), and one Mn(6) atom. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to two equivalent Ca(1), one Ti(1), and one Ti(2) atom. In the eighth O site, O(8) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Mn(1), and one Mn(4) atom to form a mixture of distorted edge, face, and corner-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 4-55°. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to two equivalent Ca(1), one Mn(2), and one Mn(5) atom. In the tenth O site, O(10) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Mn(3), and one Mn(6) atom to form a mixture of distorted edge, face, and corner-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to two equivalent Ca(1), one Ti(1), and one Mn(2) atom. In the twelfth O site, O(12) 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 edge, face, and corner-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles are 3°. In the thirteenth O site, O(13) is bonded in a 2-coordinate geometry to two equivalent Ca(1), one Ti(2), and one Mn(5) atom. In the fourteenth O site, O(14) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Mn(4), and one Mn(6) atom to form a mixture of distorted edge, face, and corner-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 6-53°.
Ca4TiMn3O11 crystallizes in the orthorhombic Pmm2 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 10-coordinate geometry to one O(10), one O(11), one O(12), one O(13), one O(14), one O(2), one O(4), one O(7), one O(8), and one O(9) atom. The Ca(1)-O(10) bond length is 2.68 Å. The Ca(1)-O(11) bond length is 2.55 Å. The Ca(1)-O(12) bond length is 2.67 Å. The Ca(1)-O(13) bond length is 2.59 Å. The Ca(1)-O(14) bond length is 2.67 Å. The Ca(1)-O(2) bond length is 2.70 Å. The Ca(1)-O(4) bond length is 2.78 Å. The Ca(1)-O(7) bond length is 2.50 Å. The Ca(1)-O(8) bond length is 2.70 Å. The Ca(1)-O(9) bond length is 2.50 Å. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(12), one O(14), one O(3), one O(5), one O(6), and one O(8) atom. The Ca(2)-O(1) bond length is 2.81 Å. The Ca(2)-O(10) bond length is 2.54 Å. The Ca(2)-O(12) bond length is 2.62 Å. The Ca(2)-O(14) bond length is 2.65 Å. The Ca(2)-O(3) bond length is 2.70 Å. The Ca(2)-O(5) bond length is 2.81 Å. The Ca(2)-O(6) bond length is 2.69 Å. The Ca(2)-O(8) bond length is 2.68 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), two equivalent O(11), and two equivalent O(7) atoms to form TiO5 trigonal bipyramids that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, and  a cornercorner with one Mn(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 13-19°. The Ti(1)-O(1) bond length is 1.76 Å. Both Ti(1)-O(11) bond lengths are 1.94 Å. Both Ti(1)-O(7) bond lengths are 1.92 Å. In the second Ti site, Ti(2) is bonded to one O(4), one O(5), two equivalent O(13), and two equivalent O(7) atoms to form TiO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, corners with two equivalent Mn(5)O5 square pyramids, and corners with two equivalent Ti(1)O5 trigonal bipyramids. The corner-sharing octahedra are not tilted. The Ti(2)-O(4) bond length is 1.85 Å. The Ti(2)-O(5) bond length is 1.98 Å. Both Ti(2)-O(13) bond lengths are 1.97 Å. Both Ti(2)-O(7) bond lengths are 2.02 Å. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), two equivalent O(12), and two equivalent O(8) atoms to form MnO5 square pyramids that share corners with two equivalent Mn(3)O6 octahedra, corners with two equivalent Mn(4)O6 octahedra, and  a cornercorner with one Ti(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 3-4°. The Mn(1)-O(1) bond length is 2.00 Å. Both Mn(1)-O(12) bond lengths are 1.92 Å. Both Mn(1)-O(8) 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(11), and two equivalent O(9) atoms to form MnO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra, corners with two equivalent Mn(5)O5 square pyramids, and corners with two equivalent Ti(1)O5 trigonal bipyramids. The corner-sharing octahedra are not tilted. The Mn(2)-O(2) bond length is 1.86 Å. The Mn(2)-O(3) bond length is 1.96 Å. Both Mn(2)-O(11) bond lengths are 1.96 Å. Both Mn(2)-O(9) bond lengths are 2.00 Å. In the third Mn site, Mn(3) is bonded to one O(2), one O(3), two equivalent O(10), and two equivalent O(12) atoms to form MnO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(1)O5 square pyramids, and corners with two equivalent Mn(6)O5 square pyramids. 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(10) bond lengths are 1.96 Å. Both Mn(3)-O(12) bond lengths are 1.95 Å. In the fourth Mn site, Mn(4) is bonded to one O(4), one O(5), two equivalent O(14), and two equivalent O(8) atoms to form MnO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Mn(1)O5 square pyramids, and corners with two equivalent Mn(6)O5 square pyramids. The corner-sharing octahedra are not tilted. The Mn(4)-O(4) bond length is 1.84 Å. The Mn(4)-O(5) bond length is 1.98 Å. Both Mn(4)-O(14) bond lengths are 1.98 Å. Both Mn(4)-O(8) bond lengths are 1.97 Å. In the fifth Mn site, Mn(5) is bonded to one O(6), two equivalent O(13), and two equivalent O(9) atoms to form MnO5 square pyramids that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, and  a cornercorner with one Mn(6)O5 square pyramid. The corner-sharing octahedral tilt angles range from 9-13°. The Mn(5)-O(6) bond length is 1.88 Å. Both Mn(5)-O(13) bond lengths are 1.91 Å. Both Mn(5)-O(9) bond lengths are 1.90 Å. In the sixth Mn site, Mn(6) is bonded to one O(6), two equivalent O(10), and two equivalent O(14) atoms to form MnO5 square pyramids that share corners with two equivalent Mn(3)O6 octahedra, corners with two equivalent Mn(4)O6 octahedra, and  a cornercorner with one Mn(5)O5 square pyramid. The corner-sharing octahedral tilt angles range from 3-8°. The Mn(6)-O(6) bond length is 1.90 Å. Both Mn(6)-O(10) bond lengths are 1.91 Å. Both Mn(6)-O(14) bond lengths are 1.89 Å. There are fourteen 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 distorted 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 and corner-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 53-55°. In the fourth O site, O(4) is bonded in a linear geometry to four equivalent Ca(1), one Ti(2), and one Mn(4) atom. In the fifth O site, O(5) is bonded in a distorted linear geometry to four equivalent Ca(2), one Ti(2), and one Mn(4) atom. In the sixth O site, O(6) is bonded in a distorted linear geometry to four equivalent Ca(2), one Mn(5), and one Mn(6) atom. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to two equivalent Ca(1), one Ti(1), and one Ti(2) atom. In the eighth O site, O(8) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Mn(1), and one Mn(4) atom to form a mixture of distorted edge, face, and corner-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 4-55°. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to two equivalent Ca(1), one Mn(2), and one Mn(5) atom. In the tenth O site, O(10) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Mn(3), and one Mn(6) atom to form a mixture of distorted edge, face, and corner-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to two equivalent Ca(1), one Ti(1), and one Mn(2) atom. In the twelfth O site, O(12) 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 edge, face, and corner-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles are 3°. In the thirteenth O site, O(13) is bonded in a 2-coordinate geometry to two equivalent Ca(1), one Ti(2), and one Mn(5) atom. In the fourteenth O site, O(14) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Mn(4), and one Mn(6) atom to form a mixture of distorted edge, face, and corner-sharing OCa4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 6-53°.