LiMn3O4 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are two 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(3) atoms to form LiO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with eight equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the second Li site, Li(2) 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 Mn(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with eight equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) 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(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with eight equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the second Mn site, Mn(2) 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(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with eight equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with six equivalent Mn(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Mn(1), one Mn(2), and two equivalent Mn(3) atoms to form OLi2Mn4 octahedra that share corners with two equivalent O(2)Li2Mn4 octahedra, corners with four equivalent O(1)Li2Mn4 octahedra, edges with four equivalent O(2)Li2Mn4 octahedra, edges with four equivalent O(3)LiMn5 octahedra, and edges with four equivalent O(4)LiMn5 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Mn(1), one Mn(2), and two equivalent Mn(3) atoms to form OLi2Mn4 octahedra that share corners with two equivalent O(1)Li2Mn4 octahedra, corners with four equivalent O(2)Li2Mn4 octahedra, edges with four equivalent O(1)Li2Mn4 octahedra, edges with four equivalent O(3)LiMn5 octahedra, and edges with four equivalent O(4)LiMn5 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded to one Li(1), one Mn(2), and four equivalent Mn(3) atoms to form OLiMn5 octahedra that share corners with two equivalent O(3)LiMn5 octahedra, corners with four equivalent O(4)LiMn5 octahedra, edges with two equivalent O(3)LiMn5 octahedra, edges with two equivalent O(4)LiMn5 octahedra, edges with four equivalent O(1)Li2Mn4 octahedra, and edges with four equivalent O(2)Li2Mn4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the fourth O site, O(4) is bonded to one Li(2), one Mn(1), and four equivalent Mn(3) atoms to form OLiMn5 octahedra that share corners with two equivalent O(4)LiMn5 octahedra, corners with four equivalent O(3)LiMn5 octahedra, edges with two equivalent O(3)LiMn5 octahedra, edges with two equivalent O(4)LiMn5 octahedra, edges with four equivalent O(1)Li2Mn4 octahedra, and edges with four equivalent O(2)Li2Mn4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°.
LiMn3O4 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are two 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(3) atoms to form LiO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with eight equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. Both Li(1)-O(1) bond lengths are 2.31 Å. Both Li(1)-O(2) bond lengths are 2.15 Å. Both Li(1)-O(3) bond lengths are 2.24 Å. In the second Li site, Li(2) 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 Mn(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with eight equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. Both Li(2)-O(1) bond lengths are 2.37 Å. Both Li(2)-O(2) bond lengths are 2.28 Å. Both Li(2)-O(4) bond lengths are 2.05 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) 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(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with eight equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. Both Mn(1)-O(1) bond lengths are 2.29 Å. Both Mn(1)-O(2) bond lengths are 2.19 Å. Both Mn(1)-O(4) bond lengths are 2.18 Å. In the second Mn site, Mn(2) 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(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with eight equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. Both Mn(2)-O(1) bond lengths are 1.98 Å. Both Mn(2)-O(2) bond lengths are 2.31 Å. Both Mn(2)-O(3) bond lengths are 2.00 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with six equivalent Mn(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. The Mn(3)-O(1) bond length is 2.15 Å. The Mn(3)-O(2) bond length is 2.09 Å. There is one shorter (2.18 Å) and one longer (2.33 Å) Mn(3)-O(3) bond length. There is one shorter (2.17 Å) and one longer (2.26 Å) Mn(3)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Mn(1), one Mn(2), and two equivalent Mn(3) atoms to form OLi2Mn4 octahedra that share corners with two equivalent O(2)Li2Mn4 octahedra, corners with four equivalent O(1)Li2Mn4 octahedra, edges with four equivalent O(2)Li2Mn4 octahedra, edges with four equivalent O(3)LiMn5 octahedra, and edges with four equivalent O(4)LiMn5 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Mn(1), one Mn(2), and two equivalent Mn(3) atoms to form OLi2Mn4 octahedra that share corners with two equivalent O(1)Li2Mn4 octahedra, corners with four equivalent O(2)Li2Mn4 octahedra, edges with four equivalent O(1)Li2Mn4 octahedra, edges with four equivalent O(3)LiMn5 octahedra, and edges with four equivalent O(4)LiMn5 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded to one Li(1), one Mn(2), and four equivalent Mn(3) atoms to form OLiMn5 octahedra that share corners with two equivalent O(3)LiMn5 octahedra, corners with four equivalent O(4)LiMn5 octahedra, edges with two equivalent O(3)LiMn5 octahedra, edges with two equivalent O(4)LiMn5 octahedra, edges with four equivalent O(1)Li2Mn4 octahedra, and edges with four equivalent O(2)Li2Mn4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the fourth O site, O(4) is bonded to one Li(2), one Mn(1), and four equivalent Mn(3) atoms to form OLiMn5 octahedra that share corners with two equivalent O(4)LiMn5 octahedra, corners with four equivalent O(3)LiMn5 octahedra, edges with two equivalent O(3)LiMn5 octahedra, edges with two equivalent O(4)LiMn5 octahedra, edges with four equivalent O(1)Li2Mn4 octahedra, and edges with four equivalent O(2)Li2Mn4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°.