Li4(NiO2)5 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(2), one O(3), and two equivalent O(1) atoms. 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(4), and one O(5) atom. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(2), one O(5), two equivalent O(3), and two equivalent O(4) atoms to form edge-sharing NiO6 octahedra. In the second Ni site, Ni(2) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form edge-sharing NiO6 octahedra. In the third Ni site, Ni(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form edge-sharing NiO6 octahedra. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Ni(3), and two equivalent Ni(2) atoms to form OLi2Ni3 trigonal bipyramids that share corners with two equivalent O(2)Li2Ni3 square pyramids, corners with two equivalent O(3)Li2Ni3 square pyramids, corners with two equivalent O(5)LiNi3 tetrahedra,  a cornercorner with one O(1)Li2Ni3 trigonal bipyramid,  an edgeedge with one O(3)Li2Ni3 square pyramid, edges with two equivalent O(2)Li2Ni3 square pyramids,  an edgeedge with one O(5)LiNi3 tetrahedra, and edges with two equivalent O(1)Li2Ni3 trigonal bipyramids. 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(3) 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 three equivalent O(5)LiNi3 tetrahedra, corners with two equivalent O(1)Li2Ni3 trigonal bipyramids, edges with two equivalent O(3)Li2Ni3 square pyramids,  an edgeedge with one O(5)LiNi3 tetrahedra, and edges with two equivalent O(1)Li2Ni3 trigonal bipyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Ni(2), and two equivalent Ni(1) atoms to form OLi2Ni3 square pyramids that share  a cornercorner with one O(2)Li2Ni3 square pyramid, corners with two equivalent O(5)LiNi3 tetrahedra, corners with two equivalent O(1)Li2Ni3 trigonal bipyramids,  an edgeedge with one O(3)Li2Ni3 square pyramid, edges with two equivalent O(2)Li2Ni3 square pyramids,  an edgeedge with one O(5)LiNi3 tetrahedra, and  an edgeedge with one O(1)Li2Ni3 trigonal bipyramid. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ni(2), and two equivalent Ni(1) atoms. In the fifth O site, O(5) is bonded to one Li(2), one Ni(1), one Ni(2), and one Ni(3) atom to form OLiNi3 tetrahedra that share corners with two equivalent O(3)Li2Ni3 square pyramids, corners with three equivalent O(2)Li2Ni3 square pyramids,  a cornercorner with one O(5)LiNi3 tetrahedra, corners with two equivalent O(1)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.
Li4(NiO2)5 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(2), one O(3), and two equivalent O(1) atoms. The Li(1)-O(2) bond length is 1.96 Å. The Li(1)-O(3) bond length is 1.99 Å. There is one shorter (1.92 Å) and one longer (2.13 Å) Li(1)-O(1) bond length. 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(4), and one O(5) atom. The Li(2)-O(2) bond length is 2.01 Å. The Li(2)-O(3) bond length is 2.03 Å. The Li(2)-O(4) bond length is 2.03 Å. The Li(2)-O(5) bond length is 1.90 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(2), one O(5), two equivalent O(3), and two equivalent O(4) atoms to form edge-sharing NiO6 octahedra. The Ni(1)-O(2) bond length is 1.89 Å. The Ni(1)-O(5) bond length is 1.94 Å. There is one shorter (1.91 Å) and one longer (1.94 Å) Ni(1)-O(3) bond length. There is one shorter (1.92 Å) and one longer (1.96 Å) Ni(1)-O(4) bond length. In the second Ni site, Ni(2) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form edge-sharing NiO6 octahedra. The Ni(2)-O(2) bond length is 1.94 Å. The Ni(2)-O(3) bond length is 2.07 Å. The Ni(2)-O(4) bond length is 1.91 Å. The Ni(2)-O(5) bond length is 1.93 Å. There is one shorter (1.91 Å) and one longer (2.08 Å) Ni(2)-O(1) bond length. In the third Ni site, Ni(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form edge-sharing NiO6 octahedra. Both Ni(3)-O(1) bond lengths are 1.90 Å. Both Ni(3)-O(2) bond lengths are 2.13 Å. Both Ni(3)-O(5) bond lengths are 1.90 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Ni(3), and two equivalent Ni(2) atoms to form OLi2Ni3 trigonal bipyramids that share corners with two equivalent O(2)Li2Ni3 square pyramids, corners with two equivalent O(3)Li2Ni3 square pyramids, corners with two equivalent O(5)LiNi3 tetrahedra,  a cornercorner with one O(1)Li2Ni3 trigonal bipyramid,  an edgeedge with one O(3)Li2Ni3 square pyramid, edges with two equivalent O(2)Li2Ni3 square pyramids,  an edgeedge with one O(5)LiNi3 tetrahedra, and edges with two equivalent O(1)Li2Ni3 trigonal bipyramids. 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(3) 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 three equivalent O(5)LiNi3 tetrahedra, corners with two equivalent O(1)Li2Ni3 trigonal bipyramids, edges with two equivalent O(3)Li2Ni3 square pyramids,  an edgeedge with one O(5)LiNi3 tetrahedra, and edges with two equivalent O(1)Li2Ni3 trigonal bipyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Ni(2), and two equivalent Ni(1) atoms to form OLi2Ni3 square pyramids that share  a cornercorner with one O(2)Li2Ni3 square pyramid, corners with two equivalent O(5)LiNi3 tetrahedra, corners with two equivalent O(1)Li2Ni3 trigonal bipyramids,  an edgeedge with one O(3)Li2Ni3 square pyramid, edges with two equivalent O(2)Li2Ni3 square pyramids,  an edgeedge with one O(5)LiNi3 tetrahedra, and  an edgeedge with one O(1)Li2Ni3 trigonal bipyramid. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ni(2), and two equivalent Ni(1) atoms. In the fifth O site, O(5) is bonded to one Li(2), one Ni(1), one Ni(2), and one Ni(3) atom to form OLiNi3 tetrahedra that share corners with two equivalent O(3)Li2Ni3 square pyramids, corners with three equivalent O(2)Li2Ni3 square pyramids,  a cornercorner with one O(5)LiNi3 tetrahedra, corners with two equivalent O(1)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.