Li3MnNi3O8 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 six equivalent Ni(1)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 Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. Mn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with six equivalent Li(1)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 Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. In the second Ni site, Ni(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form NiO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one Mn(1), and two equivalent Ni(1) atoms to form OLi3MnNi2 octahedra that share corners with six equivalent O(1)Li3MnNi2 octahedra, edges with four equivalent O(3)Li2Ni3 square pyramids, and edges with eight equivalent O(2)Li2MnNi2 square pyramids. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Mn(1), one Ni(1), and one Ni(2) atom to form OLi2MnNi2 square pyramids that share corners with two equivalent O(3)Li2Ni3 square pyramids, corners with seven equivalent O(2)Li2MnNi2 square pyramids, edges with four equivalent O(1)Li3MnNi2 octahedra, edges with two equivalent O(2)Li2MnNi2 square pyramids, and edges with two equivalent O(3)Li2Ni3 square pyramids. In the third O site, O(3) is bonded to two equivalent Li(1), one Ni(2), and two equivalent Ni(1) atoms to form OLi2Ni3 square pyramids that share corners with four equivalent O(2)Li2MnNi2 square pyramids, corners with five equivalent O(3)Li2Ni3 square pyramids, edges with four equivalent O(1)Li3MnNi2 octahedra, and edges with four equivalent O(2)Li2MnNi2 square pyramids.
Li3MnNi3O8 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 six equivalent Ni(1)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 Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. Both Li(1)-O(1) bond lengths are 2.09 Å. Both Li(1)-O(2) bond lengths are 2.10 Å. Both Li(1)-O(3) bond lengths are 2.14 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. Both Li(2)-O(1) bond lengths are 2.25 Å. All Li(2)-O(2) bond lengths are 2.16 Å. Mn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. Both Mn(1)-O(1) bond lengths are 1.94 Å. All Mn(1)-O(2) bond lengths are 1.95 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with six equivalent Li(1)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 Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. Both Ni(1)-O(1) bond lengths are 2.01 Å. Both Ni(1)-O(2) bond lengths are 2.11 Å. Both Ni(1)-O(3) bond lengths are 1.98 Å. In the second Ni site, Ni(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form NiO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. Both Ni(2)-O(3) bond lengths are 1.88 Å. All Ni(2)-O(2) bond lengths are 1.89 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one Mn(1), and two equivalent Ni(1) atoms to form OLi3MnNi2 octahedra that share corners with six equivalent O(1)Li3MnNi2 octahedra, edges with four equivalent O(3)Li2Ni3 square pyramids, and edges with eight equivalent O(2)Li2MnNi2 square pyramids. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Mn(1), one Ni(1), and one Ni(2) atom to form OLi2MnNi2 square pyramids that share corners with two equivalent O(3)Li2Ni3 square pyramids, corners with seven equivalent O(2)Li2MnNi2 square pyramids, edges with four equivalent O(1)Li3MnNi2 octahedra, edges with two equivalent O(2)Li2MnNi2 square pyramids, and edges with two equivalent O(3)Li2Ni3 square pyramids. In the third O site, O(3) is bonded to two equivalent Li(1), one Ni(2), and two equivalent Ni(1) atoms to form OLi2Ni3 square pyramids that share corners with four equivalent O(2)Li2MnNi2 square pyramids, corners with five equivalent O(3)Li2Ni3 square pyramids, edges with four equivalent O(1)Li3MnNi2 octahedra, and edges with four equivalent O(2)Li2MnNi2 square pyramids.