Li3Fe5(NiO6)2 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra, and edges with three equivalent Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-16°. In the second Li site, Li(2) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Fe(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Fe(4)O6 octahedra, edges with three equivalent Fe(3)O6 octahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-16°. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Fe(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Fe(4)O6 octahedra, edges with three equivalent Fe(2)O6 octahedra, and edges with three equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Fe(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Fe(4)O6 octahedra, edges with three equivalent Fe(1)O6 octahedra, and edges with three equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. In the third Fe site, Fe(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Fe(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Fe(4)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 7-13°. In the fourth Fe site, Fe(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form FeO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-13°. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Fe(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Fe(4)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-13°. In the second Ni site, Ni(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Fe(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Fe(4)O6 octahedra, edges with three equivalent Fe(1)O6 octahedra, and edges with three equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Fe(1), one Fe(2), one Fe(4), and one Ni(2) atom to form OLiFe3Ni square pyramids that share  a cornercorner with one O(1)LiFe3Ni square pyramid, corners with two equivalent O(3)Li2Fe2Ni square pyramids, corners with two equivalent O(6)Li2Fe2Ni square pyramids, corners with two equivalent O(2)LiFe3Ni square pyramids, corners with two equivalent O(5)LiFe3Ni square pyramids,  an edgeedge with one O(4)Li2Fe2Ni square pyramid,  an edgeedge with one O(1)LiFe3Ni square pyramid, edges with three equivalent O(2)LiFe3Ni square pyramids, and edges with three equivalent O(5)LiFe3Ni square pyramids. In the second O site, O(2) is bonded to one Li(1), one Fe(1), one Fe(2), one Fe(4), and one Ni(2) atom to form OLiFe3Ni square pyramids that share  a cornercorner with one O(2)LiFe3Ni square pyramid, corners with two equivalent O(4)Li2Fe2Ni square pyramids, corners with two equivalent O(6)Li2Fe2Ni square pyramids, corners with two equivalent O(1)LiFe3Ni square pyramids, corners with two equivalent O(5)LiFe3Ni square pyramids,  an edgeedge with one O(3)Li2Fe2Ni square pyramid,  an edgeedge with one O(2)LiFe3Ni square pyramid, edges with three equivalent O(1)LiFe3Ni square pyramids, and edges with three equivalent O(5)LiFe3Ni square pyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Fe(3), one Fe(4), and one Ni(1) atom to form OLi2Fe2Ni square pyramids that share  a cornercorner with one O(3)Li2Fe2Ni square pyramid, corners with two equivalent O(4)Li2Fe2Ni square pyramids, corners with two equivalent O(6)Li2Fe2Ni square pyramids, corners with two equivalent O(1)LiFe3Ni square pyramids, corners with two equivalent O(5)LiFe3Ni square pyramids,  an edgeedge with one O(3)Li2Fe2Ni square pyramid,  an edgeedge with one O(2)LiFe3Ni square pyramid, edges with three equivalent O(4)Li2Fe2Ni square pyramids, and edges with three equivalent O(6)Li2Fe2Ni square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Fe(3), one Fe(4), and one Ni(1) atom to form OLi2Fe2Ni square pyramids that share  a cornercorner with one O(4)Li2Fe2Ni square pyramid, corners with two equivalent O(3)Li2Fe2Ni square pyramids, corners with two equivalent O(6)Li2Fe2Ni square pyramids, corners with two equivalent O(2)LiFe3Ni square pyramids, corners with two equivalent O(5)LiFe3Ni square pyramids,  an edgeedge with one O(4)Li2Fe2Ni square pyramid,  an edgeedge with one O(1)LiFe3Ni square pyramid, edges with three equivalent O(3)Li2Fe2Ni square pyramids, and edges with three equivalent O(6)Li2Fe2Ni square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Fe(1), one Fe(2), one Fe(4), and one Ni(2) atom to form OLiFe3Ni square pyramids that share  a cornercorner with one O(5)LiFe3Ni square pyramid, corners with two equivalent O(3)Li2Fe2Ni square pyramids, corners with two equivalent O(4)Li2Fe2Ni square pyramids, corners with two equivalent O(1)LiFe3Ni square pyramids, corners with two equivalent O(2)LiFe3Ni square pyramids,  an edgeedge with one O(6)Li2Fe2Ni square pyramid,  an edgeedge with one O(5)LiFe3Ni square pyramid, edges with three equivalent O(1)LiFe3Ni square pyramids, and edges with three equivalent O(2)LiFe3Ni square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Fe(3), one Fe(4), and one Ni(1) atom to form distorted OLi2Fe2Ni square pyramids that share  a cornercorner with one O(6)Li2Fe2Ni square pyramid, corners with two equivalent O(3)Li2Fe2Ni square pyramids, corners with two equivalent O(4)Li2Fe2Ni square pyramids, corners with two equivalent O(1)LiFe3Ni square pyramids, corners with two equivalent O(2)LiFe3Ni square pyramids,  an edgeedge with one O(6)Li2Fe2Ni square pyramid,  an edgeedge with one O(5)LiFe3Ni square pyramid, edges with three equivalent O(3)Li2Fe2Ni square pyramids, and edges with three equivalent O(4)Li2Fe2Ni square pyramids.
Li3Fe5(NiO6)2 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra, and edges with three equivalent Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-16°. The Li(1)-O(1) bond length is 2.08 Å. The Li(1)-O(2) bond length is 2.10 Å. The Li(1)-O(3) bond length is 2.26 Å. The Li(1)-O(4) bond length is 2.12 Å. The Li(1)-O(5) bond length is 2.30 Å. The Li(1)-O(6) bond length is 1.98 Å. In the second Li site, Li(2) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Fe(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Fe(4)O6 octahedra, edges with three equivalent Fe(3)O6 octahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-16°. Both Li(2)-O(3) bond lengths are 2.06 Å. Both Li(2)-O(4) bond lengths are 2.15 Å. Both Li(2)-O(6) bond lengths are 2.16 Å. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Fe(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Fe(4)O6 octahedra, edges with three equivalent Fe(2)O6 octahedra, and edges with three equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. Both Fe(1)-O(1) bond lengths are 2.02 Å. Both Fe(1)-O(2) bond lengths are 2.07 Å. Both Fe(1)-O(5) bond lengths are 2.04 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Fe(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Fe(4)O6 octahedra, edges with three equivalent Fe(1)O6 octahedra, and edges with three equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. Both Fe(2)-O(1) bond lengths are 2.05 Å. Both Fe(2)-O(2) bond lengths are 2.01 Å. Both Fe(2)-O(5) bond lengths are 2.08 Å. In the third Fe site, Fe(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Fe(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Fe(4)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 7-13°. Both Fe(3)-O(3) bond lengths are 1.97 Å. Both Fe(3)-O(4) bond lengths are 2.13 Å. Both Fe(3)-O(6) bond lengths are 1.91 Å. In the fourth Fe site, Fe(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form FeO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-13°. The Fe(4)-O(1) bond length is 2.09 Å. The Fe(4)-O(2) bond length is 2.08 Å. The Fe(4)-O(3) bond length is 2.10 Å. The Fe(4)-O(4) bond length is 1.99 Å. The Fe(4)-O(5) bond length is 2.07 Å. The Fe(4)-O(6) bond length is 2.01 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Fe(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Fe(4)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-13°. Both Ni(1)-O(3) bond lengths are 1.90 Å. Both Ni(1)-O(4) bond lengths are 1.88 Å. Both Ni(1)-O(6) bond lengths are 2.27 Å. In the second Ni site, Ni(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Fe(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Fe(4)O6 octahedra, edges with three equivalent Fe(1)O6 octahedra, and edges with three equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Ni(2)-O(1) bond lengths are 2.23 Å. Both Ni(2)-O(2) bond lengths are 2.07 Å. Both Ni(2)-O(5) bond lengths are 2.03 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Fe(1), one Fe(2), one Fe(4), and one Ni(2) atom to form OLiFe3Ni square pyramids that share  a cornercorner with one O(1)LiFe3Ni square pyramid, corners with two equivalent O(3)Li2Fe2Ni square pyramids, corners with two equivalent O(6)Li2Fe2Ni square pyramids, corners with two equivalent O(2)LiFe3Ni square pyramids, corners with two equivalent O(5)LiFe3Ni square pyramids,  an edgeedge with one O(4)Li2Fe2Ni square pyramid,  an edgeedge with one O(1)LiFe3Ni square pyramid, edges with three equivalent O(2)LiFe3Ni square pyramids, and edges with three equivalent O(5)LiFe3Ni square pyramids. In the second O site, O(2) is bonded to one Li(1), one Fe(1), one Fe(2), one Fe(4), and one Ni(2) atom to form OLiFe3Ni square pyramids that share  a cornercorner with one O(2)LiFe3Ni square pyramid, corners with two equivalent O(4)Li2Fe2Ni square pyramids, corners with two equivalent O(6)Li2Fe2Ni square pyramids, corners with two equivalent O(1)LiFe3Ni square pyramids, corners with two equivalent O(5)LiFe3Ni square pyramids,  an edgeedge with one O(3)Li2Fe2Ni square pyramid,  an edgeedge with one O(2)LiFe3Ni square pyramid, edges with three equivalent O(1)LiFe3Ni square pyramids, and edges with three equivalent O(5)LiFe3Ni square pyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Fe(3), one Fe(4), and one Ni(1) atom to form OLi2Fe2Ni square pyramids that share  a cornercorner with one O(3)Li2Fe2Ni square pyramid, corners with two equivalent O(4)Li2Fe2Ni square pyramids, corners with two equivalent O(6)Li2Fe2Ni square pyramids, corners with two equivalent O(1)LiFe3Ni square pyramids, corners with two equivalent O(5)LiFe3Ni square pyramids,  an edgeedge with one O(3)Li2Fe2Ni square pyramid,  an edgeedge with one O(2)LiFe3Ni square pyramid, edges with three equivalent O(4)Li2Fe2Ni square pyramids, and edges with three equivalent O(6)Li2Fe2Ni square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Fe(3), one Fe(4), and one Ni(1) atom to form OLi2Fe2Ni square pyramids that share  a cornercorner with one O(4)Li2Fe2Ni square pyramid, corners with two equivalent O(3)Li2Fe2Ni square pyramids, corners with two equivalent O(6)Li2Fe2Ni square pyramids, corners with two equivalent O(2)LiFe3Ni square pyramids, corners with two equivalent O(5)LiFe3Ni square pyramids,  an edgeedge with one O(4)Li2Fe2Ni square pyramid,  an edgeedge with one O(1)LiFe3Ni square pyramid, edges with three equivalent O(3)Li2Fe2Ni square pyramids, and edges with three equivalent O(6)Li2Fe2Ni square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Fe(1), one Fe(2), one Fe(4), and one Ni(2) atom to form OLiFe3Ni square pyramids that share  a cornercorner with one O(5)LiFe3Ni square pyramid, corners with two equivalent O(3)Li2Fe2Ni square pyramids, corners with two equivalent O(4)Li2Fe2Ni square pyramids, corners with two equivalent O(1)LiFe3Ni square pyramids, corners with two equivalent O(2)LiFe3Ni square pyramids,  an edgeedge with one O(6)Li2Fe2Ni square pyramid,  an edgeedge with one O(5)LiFe3Ni square pyramid, edges with three equivalent O(1)LiFe3Ni square pyramids, and edges with three equivalent O(2)LiFe3Ni square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Fe(3), one Fe(4), and one Ni(1) atom to form distorted OLi2Fe2Ni square pyramids that share  a cornercorner with one O(6)Li2Fe2Ni square pyramid, corners with two equivalent O(3)Li2Fe2Ni square pyramids, corners with two equivalent O(4)Li2Fe2Ni square pyramids, corners with two equivalent O(1)LiFe3Ni square pyramids, corners with two equivalent O(2)LiFe3Ni square pyramids,  an edgeedge with one O(6)Li2Fe2Ni square pyramid,  an edgeedge with one O(5)LiFe3Ni square pyramid, edges with three equivalent O(3)Li2Fe2Ni square pyramids, and edges with three equivalent O(4)Li2Fe2Ni square pyramids.