LiMn4O8 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Cmc2_1 space group. Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(4), two equivalent O(3), and two equivalent O(6) atoms. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form a mixture of edge and corner-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. In the second Mn site, Mn(2) is bonded to one O(2), one O(5), two equivalent O(3), and two equivalent O(6) atoms to form a mixture of edge and corner-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. In the third Mn site, Mn(3) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(6) atoms to form a mixture of edge and corner-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(3) and two equivalent Mn(1) atoms. In the second O site, O(2) 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 third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom. In the fourth O site, O(4) is bonded to one Li(1), one Mn(3), and two equivalent Mn(1) atoms to form a mixture of edge and corner-sharing OLiMn3 trigonal pyramids. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Mn(2) and two equivalent Mn(1) atoms. In the sixth O site, O(6) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom to form a mixture of edge and corner-sharing OLiMn3 trigonal pyramids.
LiMn4O8 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Cmc2_1 space group. Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(4), two equivalent O(3), and two equivalent O(6) atoms. The Li(1)-O(2) bond length is 2.12 Å. The Li(1)-O(4) bond length is 1.89 Å. Both Li(1)-O(3) bond lengths are 2.45 Å. Both Li(1)-O(6) bond lengths are 2.00 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form a mixture of edge and corner-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. The Mn(1)-O(1) bond length is 1.90 Å. The Mn(1)-O(2) bond length is 1.98 Å. The Mn(1)-O(3) bond length is 1.93 Å. The Mn(1)-O(4) bond length is 1.97 Å. The Mn(1)-O(5) bond length is 1.97 Å. The Mn(1)-O(6) bond length is 1.96 Å. In the second Mn site, Mn(2) is bonded to one O(2), one O(5), two equivalent O(3), and two equivalent O(6) atoms to form a mixture of edge and corner-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. The Mn(2)-O(2) bond length is 2.05 Å. The Mn(2)-O(5) bond length is 1.94 Å. Both Mn(2)-O(3) bond lengths are 1.92 Å. Both Mn(2)-O(6) bond lengths are 1.97 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(6) atoms to form a mixture of edge and corner-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. The Mn(3)-O(1) bond length is 1.91 Å. The Mn(3)-O(4) bond length is 2.00 Å. Both Mn(3)-O(3) bond lengths are 2.07 Å. Both Mn(3)-O(6) bond lengths are 2.03 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(3) and two equivalent Mn(1) atoms. In the second O site, O(2) 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 third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom. In the fourth O site, O(4) is bonded to one Li(1), one Mn(3), and two equivalent Mn(1) atoms to form a mixture of edge and corner-sharing OLiMn3 trigonal pyramids. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Mn(2) and two equivalent Mn(1) atoms. In the sixth O site, O(6) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom to form a mixture of edge and corner-sharing OLiMn3 trigonal pyramids.