Li3Mn8O16 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form LiO4 tetrahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(4)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, and corners with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-63°. In the second Li site, Li(2) is bonded to one O(2), one O(6), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with two equivalent Mn(3)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(4)O6 octahedra, and corners with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-63°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(4)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. In the second Mn site, Mn(2) is bonded to one O(1), one O(7), two equivalent O(2), and two equivalent O(6) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. In the third Mn site, Mn(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. In the fourth Mn site, Mn(4) is bonded to one O(4), one O(6), two equivalent O(3), and two equivalent O(7) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(4)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Mn(2), and two equivalent Mn(1) atoms to form a mixture of distorted edge and corner-sharing OLiMn3 trigonal pyramids. In the second O site, O(2) is bonded to one Li(2), one Mn(1), and two equivalent Mn(2) atoms to form a mixture of distorted edge and corner-sharing OLiMn3 trigonal pyramids. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Mn(1), one Mn(3), and one Mn(4) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(4), and two equivalent Mn(3) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1) and two equivalent Mn(3) atoms. In the sixth O site, O(6) is bonded to one Li(2), one Mn(4), and two equivalent Mn(2) atoms to form a mixture of distorted edge and corner-sharing OLiMn3 trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Mn(2) and two equivalent Mn(4) atoms.
Li3Mn8O16 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form LiO4 tetrahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(4)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, and corners with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-63°. Both Li(1)-O(1) bond lengths are 1.94 Å. Both Li(1)-O(4) bond lengths are 2.03 Å. In the second Li site, Li(2) is bonded to one O(2), one O(6), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with two equivalent Mn(3)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(4)O6 octahedra, and corners with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-63°. The Li(2)-O(2) bond length is 1.98 Å. The Li(2)-O(6) bond length is 2.09 Å. Both Li(2)-O(3) bond lengths are 1.98 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(4)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The Mn(1)-O(2) bond length is 1.93 Å. The Mn(1)-O(5) bond length is 1.93 Å. Both Mn(1)-O(1) bond lengths are 2.08 Å. Both Mn(1)-O(3) bond lengths are 2.13 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(7), two equivalent O(2), and two equivalent O(6) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The Mn(2)-O(1) bond length is 1.90 Å. The Mn(2)-O(7) bond length is 1.97 Å. Both Mn(2)-O(2) bond lengths are 2.01 Å. Both Mn(2)-O(6) bond lengths are 2.03 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. Both Mn(3)-O(3) bond lengths are 1.94 Å. Both Mn(3)-O(4) bond lengths are 1.99 Å. Both Mn(3)-O(5) bond lengths are 1.96 Å. In the fourth Mn site, Mn(4) is bonded to one O(4), one O(6), two equivalent O(3), and two equivalent O(7) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(4)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The Mn(4)-O(4) bond length is 1.99 Å. The Mn(4)-O(6) bond length is 1.93 Å. Both Mn(4)-O(3) bond lengths are 1.95 Å. Both Mn(4)-O(7) bond lengths are 1.95 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Mn(2), and two equivalent Mn(1) atoms to form a mixture of distorted edge and corner-sharing OLiMn3 trigonal pyramids. In the second O site, O(2) is bonded to one Li(2), one Mn(1), and two equivalent Mn(2) atoms to form a mixture of distorted edge and corner-sharing OLiMn3 trigonal pyramids. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Mn(1), one Mn(3), and one Mn(4) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(4), and two equivalent Mn(3) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1) and two equivalent Mn(3) atoms. In the sixth O site, O(6) is bonded to one Li(2), one Mn(4), and two equivalent Mn(2) atoms to form a mixture of distorted edge and corner-sharing OLiMn3 trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Mn(2) and two equivalent Mn(4) atoms.