Li7Mn14O32 crystallizes in the trigonal R3m space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(8) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Mn(2)O6 octahedra and corners with six equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-60°. In the second Li site, Li(2) is bonded to one O(7) and three equivalent O(4) atoms to form LiO4 tetrahedra that share corners with three equivalent Mn(1)O6 octahedra and corners with six equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. In the third Li site, Li(3) is bonded to one O(6) and three equivalent O(5) atoms to form LiO4 tetrahedra that share corners with three equivalent Mn(2)O6 octahedra, corners with three equivalent Mn(4)O6 octahedra, and corners with six equivalent Mn(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-62°. In the fourth Li site, Li(4) is bonded to one O(12) and three equivalent O(10) atoms to form LiO4 tetrahedra that share corners with three equivalent Mn(6)O6 octahedra and corners with six equivalent Mn(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. In the fifth Li site, Li(5) is bonded to one O(13) and three equivalent O(9) atoms to form LiO4 tetrahedra that share corners with three equivalent Mn(4)O6 octahedra, corners with three equivalent Mn(5)O6 octahedra, and corners with six equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-62°. In the sixth Li site, Li(6) is bonded to one O(11) and three equivalent O(15) atoms to form LiO4 tetrahedra that share corners with three equivalent Mn(5)O6 octahedra and corners with six equivalent Mn(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. In the seventh Li site, Li(7) is bonded to one O(3) and three equivalent O(14) atoms to form LiO4 tetrahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(3)O6 octahedra, and corners with six equivalent Mn(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-61°. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(7), two equivalent O(1), and two equivalent O(2) atoms to form MnO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(7)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(3)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. In the second Mn site, Mn(2) is bonded to one O(6), one O(8), two equivalent O(4), and two equivalent O(9) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra,  an edgeedge with one Mn(4)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. In the third Mn site, Mn(3) is bonded to three equivalent O(1) and three equivalent O(14) atoms to form MnO6 octahedra that share corners with three equivalent Li(7)O4 tetrahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Mn(6)O6 octahedra. In the fourth Mn site, Mn(4) is bonded to three equivalent O(5) and three equivalent O(9) atoms to form MnO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(5)O4 tetrahedra, edges with three equivalent Mn(2)O6 octahedra, and edges with three equivalent Mn(5)O6 octahedra. In the fifth Mn site, Mn(5) is bonded to one O(11), one O(13), two equivalent O(10), and two equivalent O(5) atoms to form MnO6 octahedra that share  a cornercorner with one Li(5)O4 tetrahedra,  a cornercorner with one Li(6)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Mn(4)O6 octahedra, and edges with four equivalent Mn(5)O6 octahedra. In the sixth Mn site, Mn(6) is bonded to one O(12), one O(16), two equivalent O(14), and two equivalent O(15) atoms to form MnO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra, corners with two equivalent Li(7)O4 tetrahedra,  an edgeedge with one Mn(3)O6 octahedra, and edges with four equivalent Mn(6)O6 octahedra. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Mn(3) and two equivalent Mn(1) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Mn(1) atoms. In the third O site, O(3) is bonded to one Li(7) and three equivalent Mn(1) atoms to form distorted corner-sharing OLiMn3 trigonal pyramids. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2) and two equivalent Mn(2) atoms. In the fifth O site, O(5) is bonded to one Li(3), one Mn(4), and two equivalent Mn(5) atoms to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(3) and three equivalent Mn(2) atoms. In the seventh O site, O(7) is bonded to one Li(2) and three equivalent Mn(1) atoms to form distorted corner-sharing OLiMn3 trigonal pyramids. In the eighth O site, O(8) is bonded to one Li(1) and three equivalent Mn(2) atoms to form distorted edge-sharing OLiMn3 tetrahedra. In the ninth O site, O(9) is bonded to one Li(5), one Mn(4), and two equivalent Mn(2) atoms to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Li(4) and two equivalent Mn(5) atoms. In the eleventh O site, O(11) is bonded to one Li(6) and three equivalent Mn(5) atoms to form distorted edge-sharing OLiMn3 tetrahedra. In the twelfth O site, O(12) is bonded to one Li(4) and three equivalent Mn(6) atoms to form distorted edge-sharing OLiMn3 tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one Li(5) and three equivalent Mn(5) atoms. In the fourteenth O site, O(14) is bonded to one Li(7), one Mn(3), and two equivalent Mn(6) atoms to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the fifteenth O site, O(15) is bonded in a trigonal planar geometry to one Li(6) and two equivalent Mn(6) atoms. In the sixteenth O site, O(16) is bonded in a distorted T-shaped geometry to three equivalent Mn(6) atoms.
Li7Mn14O32 crystallizes in the trigonal R3m space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(8) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Mn(2)O6 octahedra and corners with six equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-60°. The Li(1)-O(8) bond length is 2.08 Å. All Li(1)-O(2) bond lengths are 1.91 Å. In the second Li site, Li(2) is bonded to one O(7) and three equivalent O(4) atoms to form LiO4 tetrahedra that share corners with three equivalent Mn(1)O6 octahedra and corners with six equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. The Li(2)-O(7) bond length is 1.97 Å. All Li(2)-O(4) bond lengths are 1.95 Å. In the third Li site, Li(3) is bonded to one O(6) and three equivalent O(5) atoms to form LiO4 tetrahedra that share corners with three equivalent Mn(2)O6 octahedra, corners with three equivalent Mn(4)O6 octahedra, and corners with six equivalent Mn(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-62°. The Li(3)-O(6) bond length is 2.04 Å. All Li(3)-O(5) bond lengths are 1.96 Å. In the fourth Li site, Li(4) is bonded to one O(12) and three equivalent O(10) atoms to form LiO4 tetrahedra that share corners with three equivalent Mn(6)O6 octahedra and corners with six equivalent Mn(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. The Li(4)-O(12) bond length is 1.97 Å. All Li(4)-O(10) bond lengths are 1.95 Å. In the fifth Li site, Li(5) is bonded to one O(13) and three equivalent O(9) atoms to form LiO4 tetrahedra that share corners with three equivalent Mn(4)O6 octahedra, corners with three equivalent Mn(5)O6 octahedra, and corners with six equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-62°. The Li(5)-O(13) bond length is 2.04 Å. All Li(5)-O(9) bond lengths are 1.96 Å. In the sixth Li site, Li(6) is bonded to one O(11) and three equivalent O(15) atoms to form LiO4 tetrahedra that share corners with three equivalent Mn(5)O6 octahedra and corners with six equivalent Mn(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. The Li(6)-O(11) bond length is 2.06 Å. All Li(6)-O(15) bond lengths are 1.92 Å. In the seventh Li site, Li(7) is bonded to one O(3) and three equivalent O(14) atoms to form LiO4 tetrahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(3)O6 octahedra, and corners with six equivalent Mn(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-61°. The Li(7)-O(3) bond length is 2.02 Å. All Li(7)-O(14) bond lengths are 1.97 Å. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(7), two equivalent O(1), and two equivalent O(2) atoms to form MnO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(7)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(3)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The Mn(1)-O(3) bond length is 1.96 Å. The Mn(1)-O(7) bond length is 1.98 Å. Both Mn(1)-O(1) bond lengths are 1.97 Å. Both Mn(1)-O(2) bond lengths are 1.87 Å. In the second Mn site, Mn(2) is bonded to one O(6), one O(8), two equivalent O(4), and two equivalent O(9) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra,  an edgeedge with one Mn(4)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The Mn(2)-O(6) bond length is 1.96 Å. The Mn(2)-O(8) bond length is 1.98 Å. Both Mn(2)-O(4) bond lengths are 1.86 Å. Both Mn(2)-O(9) bond lengths are 2.00 Å. In the third Mn site, Mn(3) is bonded to three equivalent O(1) and three equivalent O(14) atoms to form MnO6 octahedra that share corners with three equivalent Li(7)O4 tetrahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Mn(6)O6 octahedra. All Mn(3)-O(1) bond lengths are 1.92 Å. All Mn(3)-O(14) bond lengths are 1.96 Å. In the fourth Mn site, Mn(4) is bonded to three equivalent O(5) and three equivalent O(9) atoms to form MnO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(5)O4 tetrahedra, edges with three equivalent Mn(2)O6 octahedra, and edges with three equivalent Mn(5)O6 octahedra. All Mn(4)-O(5) bond lengths are 1.93 Å. All Mn(4)-O(9) bond lengths are 1.93 Å. In the fifth Mn site, Mn(5) is bonded to one O(11), one O(13), two equivalent O(10), and two equivalent O(5) atoms to form MnO6 octahedra that share  a cornercorner with one Li(5)O4 tetrahedra,  a cornercorner with one Li(6)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Mn(4)O6 octahedra, and edges with four equivalent Mn(5)O6 octahedra. The Mn(5)-O(11) bond length is 1.98 Å. The Mn(5)-O(13) bond length is 1.96 Å. Both Mn(5)-O(10) bond lengths are 1.86 Å. Both Mn(5)-O(5) bond lengths are 2.00 Å. In the sixth Mn site, Mn(6) is bonded to one O(12), one O(16), two equivalent O(14), and two equivalent O(15) atoms to form MnO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra, corners with two equivalent Li(7)O4 tetrahedra,  an edgeedge with one Mn(3)O6 octahedra, and edges with four equivalent Mn(6)O6 octahedra. The Mn(6)-O(12) bond length is 1.98 Å. The Mn(6)-O(16) bond length is 1.94 Å. Both Mn(6)-O(14) bond lengths are 1.99 Å. Both Mn(6)-O(15) bond lengths are 1.87 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Mn(3) and two equivalent Mn(1) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Mn(1) atoms. In the third O site, O(3) is bonded to one Li(7) and three equivalent Mn(1) atoms to form distorted corner-sharing OLiMn3 trigonal pyramids. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2) and two equivalent Mn(2) atoms. In the fifth O site, O(5) is bonded to one Li(3), one Mn(4), and two equivalent Mn(5) atoms to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(3) and three equivalent Mn(2) atoms. In the seventh O site, O(7) is bonded to one Li(2) and three equivalent Mn(1) atoms to form distorted corner-sharing OLiMn3 trigonal pyramids. In the eighth O site, O(8) is bonded to one Li(1) and three equivalent Mn(2) atoms to form distorted edge-sharing OLiMn3 tetrahedra. In the ninth O site, O(9) is bonded to one Li(5), one Mn(4), and two equivalent Mn(2) atoms to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Li(4) and two equivalent Mn(5) atoms. In the eleventh O site, O(11) is bonded to one Li(6) and three equivalent Mn(5) atoms to form distorted edge-sharing OLiMn3 tetrahedra. In the twelfth O site, O(12) is bonded to one Li(4) and three equivalent Mn(6) atoms to form distorted edge-sharing OLiMn3 tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one Li(5) and three equivalent Mn(5) atoms. In the fourteenth O site, O(14) is bonded to one Li(7), one Mn(3), and two equivalent Mn(6) atoms to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the fifteenth O site, O(15) is bonded in a trigonal planar geometry to one Li(6) and two equivalent Mn(6) atoms. In the sixteenth O site, O(16) is bonded in a distorted T-shaped geometry to three equivalent Mn(6) atoms.