Li5Mn3(NiO5)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-24°. In the third Li site, Li(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-16°. There are two 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(3)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. In the second Mn site, Mn(2) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form MnO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-15°. Ni(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form distorted NiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-24°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Mn(1), two equivalent Mn(2), and one Ni(1) atom to form distorted OLi2Mn3Ni octahedra that share  a cornercorner with one O(1)Li2Mn3Ni octahedra,  a cornercorner with one O(2)Li2Mn3Ni octahedra,  a cornercorner with one O(3)Li4Ni2 octahedra, corners with two equivalent O(5)Li4MnNi octahedra,  an edgeedge with one O(1)Li2Mn3Ni octahedra, edges with two equivalent O(5)Li4MnNi octahedra, edges with two equivalent O(3)Li4Ni2 octahedra, and edges with four equivalent O(2)Li2Mn3Ni octahedra. The corner-sharing octahedral tilt angles range from 0-14°. In the second O site, O(2) is bonded to two equivalent Li(2), one Mn(1), two equivalent Mn(2), and one Ni(1) atom to form OLi2Mn3Ni octahedra that share  a cornercorner with one O(1)Li2Mn3Ni octahedra,  a cornercorner with one O(2)Li2Mn3Ni octahedra,  a cornercorner with one O(5)Li4MnNi octahedra, corners with two equivalent O(3)Li4Ni2 octahedra,  an edgeedge with one O(3)Li4Ni2 octahedra, edges with two equivalent O(2)Li2Mn3Ni octahedra, edges with two equivalent O(5)Li4MnNi octahedra, and edges with four equivalent O(1)Li2Mn3Ni octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the third O site, O(3) is bonded to one Li(2), one Li(3), two equivalent Li(1), and two equivalent Ni(1) atoms to form OLi4Ni2 octahedra that share  a cornercorner with one O(1)Li2Mn3Ni octahedra,  a cornercorner with one O(5)Li4MnNi octahedra,  a cornercorner with one O(3)Li4Ni2 octahedra, corners with two equivalent O(2)Li2Mn3Ni octahedra,  an edgeedge with one O(2)Li2Mn3Ni octahedra, edges with two equivalent O(1)Li2Mn3Ni octahedra, edges with two equivalent O(3)Li4Ni2 octahedra, and edges with four equivalent O(5)Li4MnNi octahedra. The corner-sharing octahedral tilt angles range from 0-17°. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Mn(1), one Mn(2), and one Ni(1) atom. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), two equivalent Li(1), one Mn(2), and one Ni(1) atom to form OLi4MnNi octahedra that share  a cornercorner with one O(2)Li2Mn3Ni octahedra,  a cornercorner with one O(5)Li4MnNi octahedra,  a cornercorner with one O(3)Li4Ni2 octahedra, corners with two equivalent O(1)Li2Mn3Ni octahedra,  an edgeedge with one O(5)Li4MnNi octahedra, edges with two equivalent O(1)Li2Mn3Ni octahedra, edges with two equivalent O(2)Li2Mn3Ni octahedra, and edges with four equivalent O(3)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 0-17°.
Li5Mn3(NiO5)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms. The Li(1)-O(1) bond length is 2.29 Å. The Li(1)-O(4) bond length is 2.57 Å. There is one shorter (1.97 Å) and one longer (2.02 Å) Li(1)-O(3) bond length. There is one shorter (2.13 Å) and one longer (2.20 Å) Li(1)-O(5) bond length. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-24°. The Li(2)-O(1) bond length is 2.29 Å. The Li(2)-O(3) bond length is 1.91 Å. The Li(2)-O(4) bond length is 2.07 Å. The Li(2)-O(5) bond length is 1.99 Å. There is one shorter (2.31 Å) and one longer (2.44 Å) Li(2)-O(2) bond length. In the third Li site, Li(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-16°. Both Li(3)-O(3) bond lengths are 2.10 Å. Both Li(3)-O(4) bond lengths are 2.25 Å. Both Li(3)-O(5) bond lengths are 2.17 Å. There are two 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(3)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. Both Mn(1)-O(1) bond lengths are 2.02 Å. Both Mn(1)-O(2) bond lengths are 2.19 Å. Both Mn(1)-O(4) bond lengths are 1.95 Å. In the second Mn site, Mn(2) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form MnO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-15°. The Mn(2)-O(4) bond length is 1.93 Å. The Mn(2)-O(5) bond length is 1.85 Å. There is one shorter (1.98 Å) and one longer (2.05 Å) Mn(2)-O(1) bond length. There is one shorter (1.95 Å) and one longer (1.99 Å) Mn(2)-O(2) bond length. Ni(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form distorted NiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-24°. The Ni(1)-O(1) bond length is 2.35 Å. The Ni(1)-O(2) bond length is 2.18 Å. The Ni(1)-O(4) bond length is 2.14 Å. The Ni(1)-O(5) bond length is 2.07 Å. There is one shorter (1.99 Å) and one longer (2.00 Å) Ni(1)-O(3) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Mn(1), two equivalent Mn(2), and one Ni(1) atom to form distorted OLi2Mn3Ni octahedra that share  a cornercorner with one O(1)Li2Mn3Ni octahedra,  a cornercorner with one O(2)Li2Mn3Ni octahedra,  a cornercorner with one O(3)Li4Ni2 octahedra, corners with two equivalent O(5)Li4MnNi octahedra,  an edgeedge with one O(1)Li2Mn3Ni octahedra, edges with two equivalent O(5)Li4MnNi octahedra, edges with two equivalent O(3)Li4Ni2 octahedra, and edges with four equivalent O(2)Li2Mn3Ni octahedra. The corner-sharing octahedral tilt angles range from 0-14°. In the second O site, O(2) is bonded to two equivalent Li(2), one Mn(1), two equivalent Mn(2), and one Ni(1) atom to form OLi2Mn3Ni octahedra that share  a cornercorner with one O(1)Li2Mn3Ni octahedra,  a cornercorner with one O(2)Li2Mn3Ni octahedra,  a cornercorner with one O(5)Li4MnNi octahedra, corners with two equivalent O(3)Li4Ni2 octahedra,  an edgeedge with one O(3)Li4Ni2 octahedra, edges with two equivalent O(2)Li2Mn3Ni octahedra, edges with two equivalent O(5)Li4MnNi octahedra, and edges with four equivalent O(1)Li2Mn3Ni octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the third O site, O(3) is bonded to one Li(2), one Li(3), two equivalent Li(1), and two equivalent Ni(1) atoms to form OLi4Ni2 octahedra that share  a cornercorner with one O(1)Li2Mn3Ni octahedra,  a cornercorner with one O(5)Li4MnNi octahedra,  a cornercorner with one O(3)Li4Ni2 octahedra, corners with two equivalent O(2)Li2Mn3Ni octahedra,  an edgeedge with one O(2)Li2Mn3Ni octahedra, edges with two equivalent O(1)Li2Mn3Ni octahedra, edges with two equivalent O(3)Li4Ni2 octahedra, and edges with four equivalent O(5)Li4MnNi octahedra. The corner-sharing octahedral tilt angles range from 0-17°. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Mn(1), one Mn(2), and one Ni(1) atom. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), two equivalent Li(1), one Mn(2), and one Ni(1) atom to form OLi4MnNi octahedra that share  a cornercorner with one O(2)Li2Mn3Ni octahedra,  a cornercorner with one O(5)Li4MnNi octahedra,  a cornercorner with one O(3)Li4Ni2 octahedra, corners with two equivalent O(1)Li2Mn3Ni octahedra,  an edgeedge with one O(5)Li4MnNi octahedra, edges with two equivalent O(1)Li2Mn3Ni octahedra, edges with two equivalent O(2)Li2Mn3Ni octahedra, and edges with four equivalent O(3)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 0-17°.