Li5Mn2NiO8 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Ni(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)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 7-9°. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ni(1)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 8-11°. In the third Li site, Li(3) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ni(1)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 8-11°. In the fourth Li site, Li(4) 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 six equivalent Mn(1)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 Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. Mn(1) 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 six equivalent Li(4)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 Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. Ni(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form NiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)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 7-9°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(4), two equivalent Mn(1), and one Ni(1) atom to form OLi3Mn2Ni octahedra that share corners with six equivalent O(1)Li3Mn2Ni octahedra, edges with four equivalent O(2)Li4Mn2 octahedra, and edges with eight equivalent O(3)Li4MnNi octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(2), one Li(3), two equivalent Li(4), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with six equivalent O(2)Li4Mn2 octahedra, edges with four equivalent O(1)Li3Mn2Ni octahedra, and edges with eight equivalent O(3)Li4MnNi octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Ni(1) atom to form OLi4MnNi octahedra that share corners with six equivalent O(3)Li4MnNi octahedra, edges with four equivalent O(1)Li3Mn2Ni octahedra, edges with four equivalent O(2)Li4Mn2 octahedra, and edges with four equivalent O(3)Li4MnNi octahedra. The corner-sharing octahedra are not tilted.
Li5Mn2NiO8 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Ni(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)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 7-9°. Both Li(1)-O(1) bond lengths are 2.02 Å. All Li(1)-O(3) bond lengths are 2.16 Å. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ni(1)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 8-11°. Both Li(2)-O(2) bond lengths are 2.09 Å. All Li(2)-O(3) bond lengths are 2.06 Å. In the third Li site, Li(3) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ni(1)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 8-11°. Both Li(3)-O(2) bond lengths are 2.08 Å. All Li(3)-O(3) bond lengths are 2.04 Å. In the fourth Li site, Li(4) 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 six equivalent Mn(1)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 Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. Both Li(4)-O(1) bond lengths are 2.14 Å. Both Li(4)-O(2) bond lengths are 2.14 Å. Both Li(4)-O(3) bond lengths are 2.24 Å. Mn(1) 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 six equivalent Li(4)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 Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. Both Mn(1)-O(1) bond lengths are 1.95 Å. Both Mn(1)-O(2) bond lengths are 1.94 Å. Both Mn(1)-O(3) bond lengths are 1.93 Å. Ni(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form NiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)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 7-9°. Both Ni(1)-O(1) bond lengths are 2.14 Å. All Ni(1)-O(3) bond lengths are 1.93 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(4), two equivalent Mn(1), and one Ni(1) atom to form OLi3Mn2Ni octahedra that share corners with six equivalent O(1)Li3Mn2Ni octahedra, edges with four equivalent O(2)Li4Mn2 octahedra, and edges with eight equivalent O(3)Li4MnNi octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(2), one Li(3), two equivalent Li(4), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with six equivalent O(2)Li4Mn2 octahedra, edges with four equivalent O(1)Li3Mn2Ni octahedra, and edges with eight equivalent O(3)Li4MnNi octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Ni(1) atom to form OLi4MnNi octahedra that share corners with six equivalent O(3)Li4MnNi octahedra, edges with four equivalent O(1)Li3Mn2Ni octahedra, edges with four equivalent O(2)Li4Mn2 octahedra, and edges with four equivalent O(3)Li4MnNi octahedra. The corner-sharing octahedra are not tilted.