Li4(NiO2)5 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(2), one O(3), one O(5), and one O(6) atom. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(10), one O(7), one O(8), and one O(9) atom. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(1), one O(10), one O(4), and one O(9) atom. There are five inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(2), one O(3), one O(5), one O(6), one O(8), and one O(9) atom to form edge-sharing NiO6 octahedra. In the second Ni site, Ni(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form edge-sharing NiO6 octahedra. In the third Ni site, Ni(3) is bonded to one O(1), one O(10), one O(4), one O(5), one O(7), and one O(9) atom to form edge-sharing NiO6 octahedra. In the fourth Ni site, Ni(4) is bonded to one O(1), one O(10), one O(2), one O(4), one O(6), and one O(7) atom to form edge-sharing NiO6 octahedra. In the fifth Ni site, Ni(5) is bonded to one O(10), one O(3), one O(5), one O(7), one O(8), and one O(9) atom to form edge-sharing NiO6 octahedra. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(4), one Ni(2), one Ni(3), and one Ni(4) atom to form OLi2Ni3 trigonal bipyramids that share  a cornercorner with one O(10)Li2Ni3 square pyramid,  a cornercorner with one O(2)Li2Ni3 square pyramid, corners with two equivalent O(9)Li2Ni3 square pyramids, corners with two equivalent O(7)LiNi3 tetrahedra,  a cornercorner with one O(4)Li2Ni3 trigonal bipyramid,  an edgeedge with one O(10)Li2Ni3 square pyramid,  an edgeedge with one O(2)Li2Ni3 square pyramid,  an edgeedge with one O(3)Li2Ni3 square pyramid, edges with two equivalent O(4)Li2Ni3 trigonal bipyramids, and  an edgeedge with one O(6)LiNi3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Ni(1), one Ni(2), and one Ni(4) atom to form OLi2Ni3 square pyramids that share  a cornercorner with one O(10)Li2Ni3 square pyramid,  a cornercorner with one O(9)Li2Ni3 square pyramid,  a cornercorner with one O(7)LiNi3 tetrahedra,  a cornercorner with one O(1)Li2Ni3 trigonal bipyramid,  a cornercorner with one O(4)Li2Ni3 trigonal bipyramid, corners with two equivalent O(6)LiNi3 trigonal pyramids, edges with two equivalent O(3)Li2Ni3 square pyramids,  an edgeedge with one O(1)Li2Ni3 trigonal bipyramid,  an edgeedge with one O(4)Li2Ni3 trigonal bipyramid, and  an edgeedge with one O(6)LiNi3 trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Ni(1), one Ni(2), and one Ni(5) atom to form distorted OLi2Ni3 square pyramids that share  a cornercorner with one O(10)Li2Ni3 square pyramid,  a cornercorner with one O(7)LiNi3 tetrahedra, corners with two equivalent O(4)Li2Ni3 trigonal bipyramids,  a cornercorner with one O(6)LiNi3 trigonal pyramid,  an edgeedge with one O(9)Li2Ni3 square pyramid, edges with two equivalent O(2)Li2Ni3 square pyramids,  an edgeedge with one O(1)Li2Ni3 trigonal bipyramid, and  an edgeedge with one O(6)LiNi3 trigonal pyramid. In the fourth O site, O(4) is bonded to one Li(1), one Li(4), one Ni(2), one Ni(3), and one Ni(4) atom to form OLi2Ni3 trigonal bipyramids that share  a cornercorner with one O(10)Li2Ni3 square pyramid,  a cornercorner with one O(2)Li2Ni3 square pyramid, corners with two equivalent O(3)Li2Ni3 square pyramids,  a cornercorner with one O(1)Li2Ni3 trigonal bipyramid, corners with two equivalent O(6)LiNi3 trigonal pyramids,  an edgeedge with one O(10)Li2Ni3 square pyramid,  an edgeedge with one O(2)Li2Ni3 square pyramid,  an edgeedge with one O(9)Li2Ni3 square pyramid,  an edgeedge with one O(7)LiNi3 tetrahedra, and edges with two equivalent O(1)Li2Ni3 trigonal bipyramids. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ni(1), one Ni(3), and one Ni(5) atom. In the sixth O site, O(6) is bonded to one Li(2), one Ni(1), one Ni(2), and one Ni(4) atom to form distorted OLiNi3 trigonal pyramids that share  a cornercorner with one O(10)Li2Ni3 square pyramid,  a cornercorner with one O(3)Li2Ni3 square pyramid,  a cornercorner with one O(9)Li2Ni3 square pyramid, corners with two equivalent O(2)Li2Ni3 square pyramids,  a cornercorner with one O(7)LiNi3 tetrahedra, corners with two equivalent O(4)Li2Ni3 trigonal bipyramids,  an edgeedge with one O(2)Li2Ni3 square pyramid,  an edgeedge with one O(3)Li2Ni3 square pyramid, and  an edgeedge with one O(1)Li2Ni3 trigonal bipyramid. In the seventh O site, O(7) is bonded to one Li(3), one Ni(3), one Ni(4), and one Ni(5) atom to form distorted OLiNi3 tetrahedra that share  a cornercorner with one O(2)Li2Ni3 square pyramid,  a cornercorner with one O(3)Li2Ni3 square pyramid,  a cornercorner with one O(9)Li2Ni3 square pyramid, corners with two equivalent O(10)Li2Ni3 square pyramids, corners with two equivalent O(1)Li2Ni3 trigonal bipyramids,  a cornercorner with one O(6)LiNi3 trigonal pyramid,  an edgeedge with one O(10)Li2Ni3 square pyramid,  an edgeedge with one O(9)Li2Ni3 square pyramid, and  an edgeedge with one O(4)Li2Ni3 trigonal bipyramid. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), one Ni(1), one Ni(2), and one Ni(5) atom. In the ninth O site, O(9) is bonded to one Li(3), one Li(4), one Ni(1), one Ni(3), and one Ni(5) atom to form OLi2Ni3 square pyramids that share  a cornercorner with one O(2)Li2Ni3 square pyramid,  a cornercorner with one O(7)LiNi3 tetrahedra, corners with two equivalent O(1)Li2Ni3 trigonal bipyramids,  a cornercorner with one O(6)LiNi3 trigonal pyramid,  an edgeedge with one O(3)Li2Ni3 square pyramid, edges with two equivalent O(10)Li2Ni3 square pyramids,  an edgeedge with one O(7)LiNi3 tetrahedra, and  an edgeedge with one O(4)Li2Ni3 trigonal bipyramid. In the tenth O site, O(10) is bonded to one Li(3), one Li(4), one Ni(3), one Ni(4), and one Ni(5) atom to form OLi2Ni3 square pyramids that share  a cornercorner with one O(2)Li2Ni3 square pyramid,  a cornercorner with one O(3)Li2Ni3 square pyramid, corners with two equivalent O(7)LiNi3 tetrahedra,  a cornercorner with one O(1)Li2Ni3 trigonal bipyramid,  a cornercorner with one O(4)Li2Ni3 trigonal bipyramid,  a cornercorner with one O(6)LiNi3 trigonal pyramid, edges with two equivalent O(9)Li2Ni3 square pyramids,  an edgeedge with one O(7)LiNi3 tetrahedra,  an edgeedge with one O(1)Li2Ni3 trigonal bipyramid, and  an edgeedge with one O(4)Li2Ni3 trigonal bipyramid.
Li4(NiO2)5 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Li(1)-O(1) bond length is 2.12 Å. The Li(1)-O(2) bond length is 1.96 Å. The Li(1)-O(3) bond length is 2.05 Å. The Li(1)-O(4) bond length is 1.93 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(2), one O(3), one O(5), and one O(6) atom. The Li(2)-O(2) bond length is 2.02 Å. The Li(2)-O(3) bond length is 2.03 Å. The Li(2)-O(5) bond length is 2.03 Å. The Li(2)-O(6) bond length is 1.92 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(10), one O(7), one O(8), and one O(9) atom. The Li(3)-O(10) bond length is 2.04 Å. The Li(3)-O(7) bond length is 1.93 Å. The Li(3)-O(8) bond length is 2.00 Å. The Li(3)-O(9) bond length is 2.10 Å. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(1), one O(10), one O(4), and one O(9) atom. The Li(4)-O(1) bond length is 1.93 Å. The Li(4)-O(10) bond length is 1.96 Å. The Li(4)-O(4) bond length is 2.12 Å. The Li(4)-O(9) bond length is 2.05 Å. There are five inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(2), one O(3), one O(5), one O(6), one O(8), and one O(9) atom to form edge-sharing NiO6 octahedra. The Ni(1)-O(2) bond length is 1.87 Å. The Ni(1)-O(3) bond length is 2.00 Å. The Ni(1)-O(5) bond length is 2.09 Å. The Ni(1)-O(6) bond length is 2.02 Å. The Ni(1)-O(8) bond length is 1.99 Å. The Ni(1)-O(9) bond length is 1.88 Å. In the second Ni site, Ni(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form edge-sharing NiO6 octahedra. The Ni(2)-O(1) bond length is 1.90 Å. The Ni(2)-O(2) bond length is 1.92 Å. The Ni(2)-O(3) bond length is 2.12 Å. The Ni(2)-O(4) bond length is 2.18 Å. The Ni(2)-O(6) bond length is 1.89 Å. The Ni(2)-O(8) bond length is 1.91 Å. In the third Ni site, Ni(3) is bonded to one O(1), one O(10), one O(4), one O(5), one O(7), and one O(9) atom to form edge-sharing NiO6 octahedra. The Ni(3)-O(1) bond length is 2.11 Å. The Ni(3)-O(10) bond length is 1.94 Å. The Ni(3)-O(4) bond length is 1.89 Å. The Ni(3)-O(5) bond length is 1.89 Å. The Ni(3)-O(7) bond length is 1.94 Å. The Ni(3)-O(9) bond length is 2.11 Å. In the fourth Ni site, Ni(4) is bonded to one O(1), one O(10), one O(2), one O(4), one O(6), and one O(7) atom to form edge-sharing NiO6 octahedra. The Ni(4)-O(1) bond length is 1.89 Å. The Ni(4)-O(10) bond length is 2.15 Å. The Ni(4)-O(2) bond length is 2.17 Å. The Ni(4)-O(4) bond length is 1.89 Å. The Ni(4)-O(6) bond length is 1.89 Å. The Ni(4)-O(7) bond length is 1.91 Å. In the fifth Ni site, Ni(5) is bonded to one O(10), one O(3), one O(5), one O(7), one O(8), and one O(9) atom to form edge-sharing NiO6 octahedra. The Ni(5)-O(10) bond length is 1.88 Å. The Ni(5)-O(3) bond length is 1.89 Å. The Ni(5)-O(5) bond length is 1.87 Å. The Ni(5)-O(7) bond length is 1.91 Å. The Ni(5)-O(8) bond length is 1.90 Å. The Ni(5)-O(9) bond length is 1.91 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(4), one Ni(2), one Ni(3), and one Ni(4) atom to form OLi2Ni3 trigonal bipyramids that share  a cornercorner with one O(10)Li2Ni3 square pyramid,  a cornercorner with one O(2)Li2Ni3 square pyramid, corners with two equivalent O(9)Li2Ni3 square pyramids, corners with two equivalent O(7)LiNi3 tetrahedra,  a cornercorner with one O(4)Li2Ni3 trigonal bipyramid,  an edgeedge with one O(10)Li2Ni3 square pyramid,  an edgeedge with one O(2)Li2Ni3 square pyramid,  an edgeedge with one O(3)Li2Ni3 square pyramid, edges with two equivalent O(4)Li2Ni3 trigonal bipyramids, and  an edgeedge with one O(6)LiNi3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Ni(1), one Ni(2), and one Ni(4) atom to form OLi2Ni3 square pyramids that share  a cornercorner with one O(10)Li2Ni3 square pyramid,  a cornercorner with one O(9)Li2Ni3 square pyramid,  a cornercorner with one O(7)LiNi3 tetrahedra,  a cornercorner with one O(1)Li2Ni3 trigonal bipyramid,  a cornercorner with one O(4)Li2Ni3 trigonal bipyramid, corners with two equivalent O(6)LiNi3 trigonal pyramids, edges with two equivalent O(3)Li2Ni3 square pyramids,  an edgeedge with one O(1)Li2Ni3 trigonal bipyramid,  an edgeedge with one O(4)Li2Ni3 trigonal bipyramid, and  an edgeedge with one O(6)LiNi3 trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Ni(1), one Ni(2), and one Ni(5) atom to form distorted OLi2Ni3 square pyramids that share  a cornercorner with one O(10)Li2Ni3 square pyramid,  a cornercorner with one O(7)LiNi3 tetrahedra, corners with two equivalent O(4)Li2Ni3 trigonal bipyramids,  a cornercorner with one O(6)LiNi3 trigonal pyramid,  an edgeedge with one O(9)Li2Ni3 square pyramid, edges with two equivalent O(2)Li2Ni3 square pyramids,  an edgeedge with one O(1)Li2Ni3 trigonal bipyramid, and  an edgeedge with one O(6)LiNi3 trigonal pyramid. In the fourth O site, O(4) is bonded to one Li(1), one Li(4), one Ni(2), one Ni(3), and one Ni(4) atom to form OLi2Ni3 trigonal bipyramids that share  a cornercorner with one O(10)Li2Ni3 square pyramid,  a cornercorner with one O(2)Li2Ni3 square pyramid, corners with two equivalent O(3)Li2Ni3 square pyramids,  a cornercorner with one O(1)Li2Ni3 trigonal bipyramid, corners with two equivalent O(6)LiNi3 trigonal pyramids,  an edgeedge with one O(10)Li2Ni3 square pyramid,  an edgeedge with one O(2)Li2Ni3 square pyramid,  an edgeedge with one O(9)Li2Ni3 square pyramid,  an edgeedge with one O(7)LiNi3 tetrahedra, and edges with two equivalent O(1)Li2Ni3 trigonal bipyramids. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ni(1), one Ni(3), and one Ni(5) atom. In the sixth O site, O(6) is bonded to one Li(2), one Ni(1), one Ni(2), and one Ni(4) atom to form distorted OLiNi3 trigonal pyramids that share  a cornercorner with one O(10)Li2Ni3 square pyramid,  a cornercorner with one O(3)Li2Ni3 square pyramid,  a cornercorner with one O(9)Li2Ni3 square pyramid, corners with two equivalent O(2)Li2Ni3 square pyramids,  a cornercorner with one O(7)LiNi3 tetrahedra, corners with two equivalent O(4)Li2Ni3 trigonal bipyramids,  an edgeedge with one O(2)Li2Ni3 square pyramid,  an edgeedge with one O(3)Li2Ni3 square pyramid, and  an edgeedge with one O(1)Li2Ni3 trigonal bipyramid. In the seventh O site, O(7) is bonded to one Li(3), one Ni(3), one Ni(4), and one Ni(5) atom to form distorted OLiNi3 tetrahedra that share  a cornercorner with one O(2)Li2Ni3 square pyramid,  a cornercorner with one O(3)Li2Ni3 square pyramid,  a cornercorner with one O(9)Li2Ni3 square pyramid, corners with two equivalent O(10)Li2Ni3 square pyramids, corners with two equivalent O(1)Li2Ni3 trigonal bipyramids,  a cornercorner with one O(6)LiNi3 trigonal pyramid,  an edgeedge with one O(10)Li2Ni3 square pyramid,  an edgeedge with one O(9)Li2Ni3 square pyramid, and  an edgeedge with one O(4)Li2Ni3 trigonal bipyramid. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), one Ni(1), one Ni(2), and one Ni(5) atom. In the ninth O site, O(9) is bonded to one Li(3), one Li(4), one Ni(1), one Ni(3), and one Ni(5) atom to form OLi2Ni3 square pyramids that share  a cornercorner with one O(2)Li2Ni3 square pyramid,  a cornercorner with one O(7)LiNi3 tetrahedra, corners with two equivalent O(1)Li2Ni3 trigonal bipyramids,  a cornercorner with one O(6)LiNi3 trigonal pyramid,  an edgeedge with one O(3)Li2Ni3 square pyramid, edges with two equivalent O(10)Li2Ni3 square pyramids,  an edgeedge with one O(7)LiNi3 tetrahedra, and  an edgeedge with one O(4)Li2Ni3 trigonal bipyramid. In the tenth O site, O(10) is bonded to one Li(3), one Li(4), one Ni(3), one Ni(4), and one Ni(5) atom to form OLi2Ni3 square pyramids that share  a cornercorner with one O(2)Li2Ni3 square pyramid,  a cornercorner with one O(3)Li2Ni3 square pyramid, corners with two equivalent O(7)LiNi3 tetrahedra,  a cornercorner with one O(1)Li2Ni3 trigonal bipyramid,  a cornercorner with one O(4)Li2Ni3 trigonal bipyramid,  a cornercorner with one O(6)LiNi3 trigonal pyramid, edges with two equivalent O(9)Li2Ni3 square pyramids,  an edgeedge with one O(7)LiNi3 tetrahedra,  an edgeedge with one O(1)Li2Ni3 trigonal bipyramid, and  an edgeedge with one O(4)Li2Ni3 trigonal bipyramid.