Li3(NiO2)4 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Ni(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Ni(2)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 four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form NiO6 octahedra that share corners with three equivalent Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the second Ni site, Ni(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with six 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(2)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(2), one Ni(1), and two equivalent Ni(2) atoms to form OLi2Ni3 square pyramids that share corners with three equivalent O(2)Li3Ni3 octahedra, corners with two equivalent O(1)Li2Ni3 square pyramids, corners with four equivalent O(3)Li2Ni3 square pyramids, edges with three equivalent O(2)Li3Ni3 octahedra,  an edgeedge with one O(1)Li2Ni3 square pyramid, and edges with four equivalent O(3)Li2Ni3 square pyramids. The corner-sharing octahedral tilt angles range from 1-3°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Ni(1), and two equivalent Ni(2) atoms to form OLi3Ni3 octahedra that share corners with three equivalent O(2)Li3Ni3 octahedra, corners with three equivalent O(1)Li2Ni3 square pyramids,  an edgeedge with one O(2)Li3Ni3 octahedra, edges with three equivalent O(1)Li2Ni3 square pyramids, and edges with eight equivalent O(3)Li2Ni3 square pyramids. The corner-sharing octahedra are not tilted. 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 corners with two equivalent O(1)Li2Ni3 square pyramids, corners with seven equivalent O(3)Li2Ni3 square pyramids, edges with four equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(1)Li2Ni3 square pyramids, and edges with two equivalent O(3)Li2Ni3 square pyramids.
Li3(NiO2)4 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Ni(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Li(1)-O(2) bond lengths are 2.20 Å. All Li(1)-O(3) bond lengths are 2.10 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Ni(2)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 four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. Both Li(2)-O(1) bond lengths are 2.09 Å. Both Li(2)-O(2) bond lengths are 2.07 Å. Both Li(2)-O(3) bond lengths are 2.06 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form NiO6 octahedra that share corners with three equivalent Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. The Ni(1)-O(1) bond length is 1.86 Å. The Ni(1)-O(2) bond length is 1.91 Å. There are two shorter (1.86 Å) and two longer (1.90 Å) Ni(1)-O(3) bond lengths. In the second Ni site, Ni(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with six 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(2)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. Both Ni(2)-O(1) bond lengths are 1.93 Å. Both Ni(2)-O(2) bond lengths are 1.95 Å. Both Ni(2)-O(3) bond lengths are 2.08 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(2), one Ni(1), and two equivalent Ni(2) atoms to form OLi2Ni3 square pyramids that share corners with three equivalent O(2)Li3Ni3 octahedra, corners with two equivalent O(1)Li2Ni3 square pyramids, corners with four equivalent O(3)Li2Ni3 square pyramids, edges with three equivalent O(2)Li3Ni3 octahedra,  an edgeedge with one O(1)Li2Ni3 square pyramid, and edges with four equivalent O(3)Li2Ni3 square pyramids. The corner-sharing octahedral tilt angles range from 1-3°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Ni(1), and two equivalent Ni(2) atoms to form OLi3Ni3 octahedra that share corners with three equivalent O(2)Li3Ni3 octahedra, corners with three equivalent O(1)Li2Ni3 square pyramids,  an edgeedge with one O(2)Li3Ni3 octahedra, edges with three equivalent O(1)Li2Ni3 square pyramids, and edges with eight equivalent O(3)Li2Ni3 square pyramids. The corner-sharing octahedra are not tilted. 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 corners with two equivalent O(1)Li2Ni3 square pyramids, corners with seven equivalent O(3)Li2Ni3 square pyramids, edges with four equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(1)Li2Ni3 square pyramids, and edges with two equivalent O(3)Li2Ni3 square pyramids.