Li4(NiO2)7 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(4), one O(6), and two equivalent O(2) atoms to form LiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent Ni(3)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-15°. In the second Li site, Li(2) is bonded to one O(4), one O(6), two equivalent O(5), and two equivalent O(7) atoms to form LiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(4)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, corners with two equivalent Ni(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom to form NiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with three equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. In the second Ni site, Ni(2) is bonded to one O(1), one O(2), one O(5), one O(7), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with three equivalent Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-14°. In the third Ni site, Ni(3) is bonded to one O(2), one O(7), two equivalent O(3), and two equivalent O(4) atoms to form NiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-15°. In the fourth Ni site, Ni(4) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with four equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a see-saw-like geometry to one Li(1), one Ni(1), one Ni(2), and one Ni(4) atom. In the second O site, O(2) is bonded to two equivalent Li(1), one Ni(1), one Ni(2), and one Ni(3) atom to form a mixture of edge and corner-sharing OLi2Ni3 square pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ni(1), and two equivalent Ni(3) atoms. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Ni(1), and two equivalent Ni(3) atoms to form a mixture of edge and corner-sharing OLi2Ni3 square pyramids. In the fifth O site, O(5) is bonded to two equivalent Li(2), one Ni(1), one Ni(2), and one Ni(4) atom to form a mixture of edge and corner-sharing OLi2Ni3 square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Ni(4), and two equivalent Ni(2) atoms to form a mixture of edge and corner-sharing OLi2Ni3 square pyramids. In the seventh O site, O(7) is bonded to two equivalent Li(2), one Ni(1), one Ni(2), and one Ni(3) atom to form a mixture of edge and corner-sharing OLi2Ni3 square pyramids.
Li4(NiO2)7 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(4), one O(6), and two equivalent O(2) atoms to form LiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent Ni(3)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-15°. The Li(1)-O(1) bond length is 2.10 Å. The Li(1)-O(3) bond length is 2.13 Å. The Li(1)-O(4) bond length is 2.14 Å. The Li(1)-O(6) bond length is 2.14 Å. There is one shorter (2.11 Å) and one longer (2.13 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded to one O(4), one O(6), two equivalent O(5), and two equivalent O(7) atoms to form LiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(4)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, corners with two equivalent Ni(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. The Li(2)-O(4) bond length is 2.07 Å. The Li(2)-O(6) bond length is 2.11 Å. There is one shorter (2.11 Å) and one longer (2.17 Å) Li(2)-O(5) bond length. There is one shorter (2.08 Å) and one longer (2.15 Å) Li(2)-O(7) bond length. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom to form NiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with three equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. The Ni(1)-O(1) bond length is 1.88 Å. The Ni(1)-O(2) bond length is 1.87 Å. The Ni(1)-O(3) bond length is 1.89 Å. The Ni(1)-O(4) bond length is 1.89 Å. The Ni(1)-O(5) bond length is 1.88 Å. The Ni(1)-O(7) bond length is 1.89 Å. In the second Ni site, Ni(2) is bonded to one O(1), one O(2), one O(5), one O(7), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with three equivalent Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-14°. The Ni(2)-O(1) bond length is 1.98 Å. The Ni(2)-O(2) bond length is 2.03 Å. The Ni(2)-O(5) bond length is 2.01 Å. The Ni(2)-O(7) bond length is 1.85 Å. There is one shorter (1.87 Å) and one longer (2.05 Å) Ni(2)-O(6) bond length. In the third Ni site, Ni(3) is bonded to one O(2), one O(7), two equivalent O(3), and two equivalent O(4) atoms to form NiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-15°. The Ni(3)-O(2) bond length is 1.90 Å. The Ni(3)-O(7) bond length is 2.10 Å. There is one shorter (1.90 Å) and one longer (1.92 Å) Ni(3)-O(3) bond length. There is one shorter (1.90 Å) and one longer (2.08 Å) Ni(3)-O(4) bond length. In the fourth Ni site, Ni(4) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with four equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. Both Ni(4)-O(1) bond lengths are 1.89 Å. Both Ni(4)-O(5) bond lengths are 1.89 Å. Both Ni(4)-O(6) bond lengths are 1.87 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a see-saw-like geometry to one Li(1), one Ni(1), one Ni(2), and one Ni(4) atom. In the second O site, O(2) is bonded to two equivalent Li(1), one Ni(1), one Ni(2), and one Ni(3) atom to form a mixture of edge and corner-sharing OLi2Ni3 square pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ni(1), and two equivalent Ni(3) atoms. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Ni(1), and two equivalent Ni(3) atoms to form a mixture of edge and corner-sharing OLi2Ni3 square pyramids. In the fifth O site, O(5) is bonded to two equivalent Li(2), one Ni(1), one Ni(2), and one Ni(4) atom to form a mixture of edge and corner-sharing OLi2Ni3 square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Ni(4), and two equivalent Ni(2) atoms to form a mixture of edge and corner-sharing OLi2Ni3 square pyramids. In the seventh O site, O(7) is bonded to two equivalent Li(2), one Ni(1), one Ni(2), and one Ni(3) atom to form a mixture of edge and corner-sharing OLi2Ni3 square pyramids.