Li6(NiO2)5 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Ni(3)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, corners with two equivalent Li(2)O4 trigonal pyramids,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 6-70°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 trigonal pyramids that share corners with three equivalent Ni(1)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 2-72°. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(3), one O(4), and two equivalent O(5) atoms. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form NiO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 trigonal pyramids,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, edges with three equivalent Ni(2)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. In the second Ni site, Ni(2) is bonded to one O(3), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form NiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 trigonal pyramids,  an edgeedge with one Ni(3)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with three equivalent Ni(1)O6 octahedra, edges with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. In the third Ni site, Ni(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, edges with two equivalent Ni(2)O6 octahedra, edges with four equivalent Ni(1)O6 octahedra, and edges with two equivalent Li(2)O4 trigonal pyramids. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Ni(1), and two equivalent Ni(2) atoms to form distorted OLi2Ni3 trigonal bipyramids that share  a cornercorner with one O(3)Li3Ni3 octahedra, corners with two equivalent O(2)Li3Ni3 octahedra, corners with three equivalent O(4)Li2Ni3 square pyramids, corners with three equivalent O(5)Li2Ni3 square pyramids, edges with two equivalent O(3)Li3Ni3 octahedra, edges with three equivalent O(2)Li3Ni3 octahedra, and  an edgeedge with one O(1)Li2Ni3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 8-86°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), one Ni(1), and two equivalent Ni(2) atoms to form OLi3Ni3 octahedra that share corners with two equivalent O(3)Li3Ni3 octahedra,  a cornercorner with one O(4)Li2Ni3 square pyramid,  a cornercorner with one O(5)Li2Ni3 square pyramid, corners with two equivalent O(1)Li2Ni3 trigonal bipyramids, edges with two equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(3)Li3Ni3 octahedra,  an edgeedge with one O(4)Li2Ni3 square pyramid,  an edgeedge with one O(5)Li2Ni3 square pyramid, and edges with three equivalent O(1)Li2Ni3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-48°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Ni(1), one Ni(2), and one Ni(3) atom to form OLi3Ni3 octahedra that share  a cornercorner with one O(3)Li3Ni3 octahedra, corners with two equivalent O(2)Li3Ni3 octahedra, corners with two equivalent O(5)Li2Ni3 square pyramids,  a cornercorner with one O(1)Li2Ni3 trigonal bipyramid, edges with two equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(5)Li2Ni3 square pyramids, edges with three equivalent O(4)Li2Ni3 square pyramids, and edges with two equivalent O(1)Li2Ni3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-48°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Ni(3), and two equivalent Ni(1) atoms to form OLi2Ni3 square pyramids that share  a cornercorner with one O(2)Li3Ni3 octahedra,  a cornercorner with one O(4)Li2Ni3 square pyramid, corners with two equivalent O(5)Li2Ni3 square pyramids, corners with three equivalent O(1)Li2Ni3 trigonal bipyramids,  an edgeedge with one O(2)Li3Ni3 octahedra, edges with three equivalent O(3)Li3Ni3 octahedra,  an edgeedge with one O(4)Li2Ni3 square pyramid, and edges with two equivalent O(5)Li2Ni3 square pyramids. The corner-sharing octahedral tilt angles are 7°. In the fifth O site, O(5) is bonded to two equivalent Li(3), one Ni(1), one Ni(2), and one Ni(3) atom to form distorted OLi2Ni3 square pyramids that share  a cornercorner with one O(2)Li3Ni3 octahedra, corners with two equivalent O(3)Li3Ni3 octahedra,  a cornercorner with one O(5)Li2Ni3 square pyramid, corners with two equivalent O(4)Li2Ni3 square pyramids, corners with three equivalent O(1)Li2Ni3 trigonal bipyramids,  an edgeedge with one O(2)Li3Ni3 octahedra, edges with two equivalent O(3)Li3Ni3 octahedra,  an edgeedge with one O(5)Li2Ni3 square pyramid, and edges with two equivalent O(4)Li2Ni3 square pyramids. The corner-sharing octahedral tilt angles range from 5-78°.
Li6(NiO2)5 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Ni(3)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, corners with two equivalent Li(2)O4 trigonal pyramids,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 6-70°. The Li(1)-O(1) bond length is 1.96 Å. The Li(1)-O(3) bond length is 1.86 Å. There is one shorter (1.94 Å) and one longer (2.07 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 trigonal pyramids that share corners with three equivalent Ni(1)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 2-72°. The Li(2)-O(1) bond length is 1.91 Å. The Li(2)-O(2) bond length is 2.05 Å. The Li(2)-O(3) bond length is 1.94 Å. The Li(2)-O(4) bond length is 1.94 Å. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(3), one O(4), and two equivalent O(5) atoms. The Li(3)-O(3) bond length is 1.92 Å. The Li(3)-O(4) bond length is 1.89 Å. There is one shorter (1.88 Å) and one longer (2.11 Å) Li(3)-O(5) bond length. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form NiO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 trigonal pyramids,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, edges with three equivalent Ni(2)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The Ni(1)-O(1) bond length is 1.91 Å. The Ni(1)-O(2) bond length is 1.96 Å. The Ni(1)-O(3) bond length is 2.11 Å. The Ni(1)-O(5) bond length is 2.07 Å. There is one shorter (1.91 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(3), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form NiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 trigonal pyramids,  an edgeedge with one Ni(3)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with three equivalent Ni(1)O6 octahedra, edges with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The Ni(2)-O(3) bond length is 2.08 Å. The Ni(2)-O(5) bond length is 2.03 Å. There is one shorter (2.08 Å) and one longer (2.10 Å) Ni(2)-O(1) bond length. There is one shorter (2.07 Å) and one longer (2.16 Å) Ni(2)-O(2) bond length. In the third Ni site, Ni(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, edges with two equivalent Ni(2)O6 octahedra, edges with four equivalent Ni(1)O6 octahedra, and edges with two equivalent Li(2)O4 trigonal pyramids. Both Ni(3)-O(3) bond lengths are 1.92 Å. Both Ni(3)-O(4) bond lengths are 2.09 Å. Both Ni(3)-O(5) bond lengths are 1.91 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Ni(1), and two equivalent Ni(2) atoms to form distorted OLi2Ni3 trigonal bipyramids that share  a cornercorner with one O(3)Li3Ni3 octahedra, corners with two equivalent O(2)Li3Ni3 octahedra, corners with three equivalent O(4)Li2Ni3 square pyramids, corners with three equivalent O(5)Li2Ni3 square pyramids, edges with two equivalent O(3)Li3Ni3 octahedra, edges with three equivalent O(2)Li3Ni3 octahedra, and  an edgeedge with one O(1)Li2Ni3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 8-86°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), one Ni(1), and two equivalent Ni(2) atoms to form OLi3Ni3 octahedra that share corners with two equivalent O(3)Li3Ni3 octahedra,  a cornercorner with one O(4)Li2Ni3 square pyramid,  a cornercorner with one O(5)Li2Ni3 square pyramid, corners with two equivalent O(1)Li2Ni3 trigonal bipyramids, edges with two equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(3)Li3Ni3 octahedra,  an edgeedge with one O(4)Li2Ni3 square pyramid,  an edgeedge with one O(5)Li2Ni3 square pyramid, and edges with three equivalent O(1)Li2Ni3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-48°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Ni(1), one Ni(2), and one Ni(3) atom to form OLi3Ni3 octahedra that share  a cornercorner with one O(3)Li3Ni3 octahedra, corners with two equivalent O(2)Li3Ni3 octahedra, corners with two equivalent O(5)Li2Ni3 square pyramids,  a cornercorner with one O(1)Li2Ni3 trigonal bipyramid, edges with two equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(5)Li2Ni3 square pyramids, edges with three equivalent O(4)Li2Ni3 square pyramids, and edges with two equivalent O(1)Li2Ni3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-48°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Ni(3), and two equivalent Ni(1) atoms to form OLi2Ni3 square pyramids that share  a cornercorner with one O(2)Li3Ni3 octahedra,  a cornercorner with one O(4)Li2Ni3 square pyramid, corners with two equivalent O(5)Li2Ni3 square pyramids, corners with three equivalent O(1)Li2Ni3 trigonal bipyramids,  an edgeedge with one O(2)Li3Ni3 octahedra, edges with three equivalent O(3)Li3Ni3 octahedra,  an edgeedge with one O(4)Li2Ni3 square pyramid, and edges with two equivalent O(5)Li2Ni3 square pyramids. The corner-sharing octahedral tilt angles are 7°. In the fifth O site, O(5) is bonded to two equivalent Li(3), one Ni(1), one Ni(2), and one Ni(3) atom to form distorted OLi2Ni3 square pyramids that share  a cornercorner with one O(2)Li3Ni3 octahedra, corners with two equivalent O(3)Li3Ni3 octahedra,  a cornercorner with one O(5)Li2Ni3 square pyramid, corners with two equivalent O(4)Li2Ni3 square pyramids, corners with three equivalent O(1)Li2Ni3 trigonal bipyramids,  an edgeedge with one O(2)Li3Ni3 octahedra, edges with two equivalent O(3)Li3Ni3 octahedra,  an edgeedge with one O(5)Li2Ni3 square pyramid, and edges with two equivalent O(4)Li2Ni3 square pyramids. The corner-sharing octahedral tilt angles range from 5-78°.