Li3Mn3NiO8 crystallizes in the triclinic P-1 space group. There are three 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(4) atoms to form LiO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. In the second Li site, Li(2) 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(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-14°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) 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 Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. In the second Mn site, Mn(2) 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 six 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 Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. In the third Mn site, Mn(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share 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 Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. 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(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-14°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Mn(1), one Mn(2), 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)Li2Mn2Ni square pyramids, edges with four equivalent O(3)Li2Mn2Ni square pyramids, and edges with four equivalent O(4)Li2Mn3 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(2), one Mn(3), and one Ni(1) atom to form OLi2Mn2Ni square pyramids that share corners with two equivalent O(3)Li2Mn2Ni square pyramids, corners with two equivalent O(4)Li2Mn3 square pyramids, corners with five equivalent O(2)Li2Mn2Ni square pyramids, edges with four equivalent O(1)Li3Mn2Ni octahedra, edges with two equivalent O(3)Li2Mn2Ni square pyramids, and edges with two equivalent O(4)Li2Mn3 square pyramids. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Mn(1), one Mn(3), and one Ni(1) atom to form OLi2Mn2Ni square pyramids that share corners with two equivalent O(2)Li2Mn2Ni square pyramids, corners with two equivalent O(4)Li2Mn3 square pyramids, corners with five equivalent O(3)Li2Mn2Ni square pyramids, edges with four equivalent O(1)Li3Mn2Ni octahedra, edges with two equivalent O(2)Li2Mn2Ni square pyramids, and edges with two equivalent O(4)Li2Mn3 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Mn(1), one Mn(2), and one Mn(3) atom to form OLi2Mn3 square pyramids that share corners with two equivalent O(2)Li2Mn2Ni square pyramids, corners with two equivalent O(3)Li2Mn2Ni square pyramids, corners with five equivalent O(4)Li2Mn3 square pyramids, edges with four equivalent O(1)Li3Mn2Ni octahedra, edges with two equivalent O(2)Li2Mn2Ni square pyramids, and edges with two equivalent O(3)Li2Mn2Ni square pyramids.
Li3Mn3NiO8 crystallizes in the triclinic P-1 space group. There are three 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(4) atoms to form LiO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. Both Li(1)-O(1) bond lengths are 2.18 Å. Both Li(1)-O(2) bond lengths are 2.19 Å. Both Li(1)-O(4) bond lengths are 2.06 Å. In the second Li site, Li(2) 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(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-14°. Both Li(2)-O(1) bond lengths are 2.08 Å. Both Li(2)-O(2) bond lengths are 2.10 Å. Both Li(2)-O(3) bond lengths are 2.17 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) 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 Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. Both Li(3)-O(1) bond lengths are 2.33 Å. Both Li(3)-O(3) bond lengths are 2.17 Å. Both Li(3)-O(4) bond lengths are 2.19 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. Both Mn(1)-O(1) bond lengths are 1.96 Å. Both Mn(1)-O(3) bond lengths are 1.96 Å. Both Mn(1)-O(4) bond lengths are 1.95 Å. In the second Mn site, Mn(2) 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 six 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 Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. Both Mn(2)-O(1) bond lengths are 1.97 Å. Both Mn(2)-O(2) bond lengths are 1.95 Å. Both Mn(2)-O(4) bond lengths are 2.25 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share 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 Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. Both Mn(3)-O(2) bond lengths are 1.93 Å. Both Mn(3)-O(3) bond lengths are 1.93 Å. Both Mn(3)-O(4) bond lengths are 1.93 Å. 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(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-14°. Both Ni(1)-O(1) bond lengths are 2.06 Å. Both Ni(1)-O(2) bond lengths are 2.06 Å. Both Ni(1)-O(3) bond lengths are 2.13 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Mn(1), one Mn(2), 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)Li2Mn2Ni square pyramids, edges with four equivalent O(3)Li2Mn2Ni square pyramids, and edges with four equivalent O(4)Li2Mn3 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(2), one Mn(3), and one Ni(1) atom to form OLi2Mn2Ni square pyramids that share corners with two equivalent O(3)Li2Mn2Ni square pyramids, corners with two equivalent O(4)Li2Mn3 square pyramids, corners with five equivalent O(2)Li2Mn2Ni square pyramids, edges with four equivalent O(1)Li3Mn2Ni octahedra, edges with two equivalent O(3)Li2Mn2Ni square pyramids, and edges with two equivalent O(4)Li2Mn3 square pyramids. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Mn(1), one Mn(3), and one Ni(1) atom to form OLi2Mn2Ni square pyramids that share corners with two equivalent O(2)Li2Mn2Ni square pyramids, corners with two equivalent O(4)Li2Mn3 square pyramids, corners with five equivalent O(3)Li2Mn2Ni square pyramids, edges with four equivalent O(1)Li3Mn2Ni octahedra, edges with two equivalent O(2)Li2Mn2Ni square pyramids, and edges with two equivalent O(4)Li2Mn3 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Mn(1), one Mn(2), and one Mn(3) atom to form OLi2Mn3 square pyramids that share corners with two equivalent O(2)Li2Mn2Ni square pyramids, corners with two equivalent O(3)Li2Mn2Ni square pyramids, corners with five equivalent O(4)Li2Mn3 square pyramids, edges with four equivalent O(1)Li3Mn2Ni octahedra, edges with two equivalent O(2)Li2Mn2Ni square pyramids, and edges with two equivalent O(3)Li2Mn2Ni square pyramids.