Li9Mn7O16 is Caswellsilverite-like structured and crystallizes in the monoclinic P2/m space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Li(6)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(4)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(5)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-15°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Mn(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(4)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. In the fourth Li site, Li(4) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. In the fifth Li site, Li(5) is bonded to two equivalent O(5) and four equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Li(6)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, edges with four equivalent Li(4)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-14°. In the sixth Li site, Li(6) is bonded to two equivalent O(5) and four equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Li(5)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(4)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-15°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(4)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(5)O6 octahedra,  an edgeedge with one Li(6)O6 octahedra,  an edgeedge with one Mn(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-14°. In the third Mn site, Mn(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Li(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. In the fourth Mn site, Mn(4) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(4), one Mn(1), one Mn(2), and one Mn(3) atom to form OLi3Mn3 octahedra that share corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(3)Li3Mn3 octahedra, corners with two equivalent O(5)Li4Mn2 octahedra,  an edgeedge with one O(3)Li3Mn3 octahedra,  an edgeedge with one O(5)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, and edges with four equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Mn(2), one Mn(3), and one Mn(4) atom to form OLi3Mn3 octahedra that share corners with two equivalent O(4)Li4Mn2 octahedra, corners with four equivalent O(2)Li3Mn3 octahedra,  an edgeedge with one O(4)Li4Mn2 octahedra, edges with three equivalent O(2)Li3Mn3 octahedra, edges with four equivalent O(1)Li3Mn3 octahedra, and edges with four equivalent O(3)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(2), one Mn(4), and two equivalent Mn(3) atoms to form a mixture of edge and corner-sharing OLi3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth O site, O(4) is bonded to one Li(1), one Li(4), one Li(5), one Li(6), one Mn(1), and one Mn(2) atom to form distorted OLi4Mn2 octahedra that share corners with two equivalent O(2)Li3Mn3 octahedra, corners with four equivalent O(4)Li4Mn2 octahedra,  an edgeedge with one O(2)Li3Mn3 octahedra, edges with three equivalent O(4)Li4Mn2 octahedra, edges with four equivalent O(1)Li3Mn3 octahedra, and edges with four equivalent O(5)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fifth O site, O(5) is bonded to one Li(5), one Li(6), two equivalent Li(4), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with two equivalent O(5)Li4Mn2 octahedra, corners with four equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li4Mn2 octahedra, and edges with eight equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°.
Li9Mn7O16 is Caswellsilverite-like structured and crystallizes in the monoclinic P2/m space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Li(6)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(4)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(5)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-15°. Both Li(1)-O(1) bond lengths are 2.18 Å. Both Li(1)-O(2) bond lengths are 2.15 Å. Both Li(1)-O(4) bond lengths are 2.06 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Mn(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. Both Li(2)-O(1) bond lengths are 2.16 Å. Both Li(2)-O(2) bond lengths are 2.18 Å. Both Li(2)-O(3) bond lengths are 2.13 Å. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(4)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. Both Li(3)-O(3) bond lengths are 2.16 Å. All Li(3)-O(2) bond lengths are 2.14 Å. In the fourth Li site, Li(4) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Both Li(4)-O(1) bond lengths are 2.13 Å. Both Li(4)-O(4) bond lengths are 2.47 Å. Both Li(4)-O(5) bond lengths are 2.11 Å. In the fifth Li site, Li(5) is bonded to two equivalent O(5) and four equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Li(6)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, edges with four equivalent Li(4)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-14°. Both Li(5)-O(5) bond lengths are 2.15 Å. All Li(5)-O(4) bond lengths are 2.15 Å. In the sixth Li site, Li(6) is bonded to two equivalent O(5) and four equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Li(5)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(4)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-15°. Both Li(6)-O(5) bond lengths are 2.30 Å. All Li(6)-O(4) bond lengths are 2.05 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(4)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. Both Mn(1)-O(1) bond lengths are 1.95 Å. Both Mn(1)-O(4) bond lengths are 1.97 Å. Both Mn(1)-O(5) bond lengths are 1.94 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(5)O6 octahedra,  an edgeedge with one Li(6)O6 octahedra,  an edgeedge with one Mn(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-14°. Both Mn(2)-O(1) bond lengths are 2.27 Å. Both Mn(2)-O(2) bond lengths are 1.98 Å. Both Mn(2)-O(4) bond lengths are 1.94 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Li(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. Both Mn(3)-O(1) bond lengths are 1.98 Å. Both Mn(3)-O(2) bond lengths are 2.26 Å. Both Mn(3)-O(3) bond lengths are 1.96 Å. In the fourth Mn site, Mn(4) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Both Mn(4)-O(3) bond lengths are 2.28 Å. All Mn(4)-O(2) bond lengths are 1.96 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(4), one Mn(1), one Mn(2), and one Mn(3) atom to form OLi3Mn3 octahedra that share corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(3)Li3Mn3 octahedra, corners with two equivalent O(5)Li4Mn2 octahedra,  an edgeedge with one O(3)Li3Mn3 octahedra,  an edgeedge with one O(5)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, and edges with four equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Mn(2), one Mn(3), and one Mn(4) atom to form OLi3Mn3 octahedra that share corners with two equivalent O(4)Li4Mn2 octahedra, corners with four equivalent O(2)Li3Mn3 octahedra,  an edgeedge with one O(4)Li4Mn2 octahedra, edges with three equivalent O(2)Li3Mn3 octahedra, edges with four equivalent O(1)Li3Mn3 octahedra, and edges with four equivalent O(3)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(2), one Mn(4), and two equivalent Mn(3) atoms to form a mixture of edge and corner-sharing OLi3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth O site, O(4) is bonded to one Li(1), one Li(4), one Li(5), one Li(6), one Mn(1), and one Mn(2) atom to form distorted OLi4Mn2 octahedra that share corners with two equivalent O(2)Li3Mn3 octahedra, corners with four equivalent O(4)Li4Mn2 octahedra,  an edgeedge with one O(2)Li3Mn3 octahedra, edges with three equivalent O(4)Li4Mn2 octahedra, edges with four equivalent O(1)Li3Mn3 octahedra, and edges with four equivalent O(5)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fifth O site, O(5) is bonded to one Li(5), one Li(6), two equivalent Li(4), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with two equivalent O(5)Li4Mn2 octahedra, corners with four equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li4Mn2 octahedra, and edges with eight equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°.