CsLi7(NiO3)2 crystallizes in the monoclinic C2/m space group. Cs(1) is bonded in a 22-coordinate geometry to two equivalent Li(1), six equivalent Li(2), four equivalent Ni(1), four equivalent O(1), and six equivalent O(3) atoms. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one Cs(1), one O(2), one O(3), and two equivalent O(1) atoms to form distorted LiCsO4 trigonal pyramids that share  a cornercorner with one Li(3)O4 tetrahedra, corners with three equivalent Li(2)Cs3O4 trigonal pyramids, corners with three equivalent Li(1)CsO4 trigonal pyramids, edges with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Li(2)Cs3O4 trigonal pyramid, and faces with two equivalent Li(2)Cs3O4 trigonal pyramids. In the second Li site, Li(2) is bonded to three equivalent Cs(1), one O(1), and three equivalent O(3) atoms to form distorted LiCs3O4 trigonal pyramids that share  a cornercorner with one Li(3)O4 tetrahedra, corners with three equivalent Li(1)CsO4 trigonal pyramids, corners with seven equivalent Li(2)Cs3O4 trigonal pyramids,  an edgeedge with one Li(1)CsO4 trigonal pyramid, edges with three equivalent Li(2)Cs3O4 trigonal pyramids, faces with two equivalent Li(2)Cs3O4 trigonal pyramids, and faces with two equivalent Li(1)CsO4 trigonal pyramids. In the third Li site, Li(3) is bonded to one O(1) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra,  a cornercorner with one Li(2)Cs3O4 trigonal pyramid,  a cornercorner with one Li(1)CsO4 trigonal pyramid, edges with two equivalent Li(3)O4 tetrahedra, and edges with two equivalent Li(1)CsO4 trigonal pyramids. In the fourth Li site, Li(4) is bonded in a linear geometry to two equivalent O(2) atoms. Ni(1) is bonded in a trigonal planar geometry to two equivalent Cs(1), one O(1), one O(2), and one O(3) atom. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one Li(2), one Li(3), two equivalent Li(1), and one Ni(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(4), three equivalent Li(3), and one Ni(1) atom to form a mixture of distorted corner and edge-sharing OLi5Ni octahedra. The corner-sharing octahedral tilt angles range from 0-46°. In the third O site, O(3) is bonded in a 5-coordinate geometry to three equivalent Cs(1), one Li(1), three equivalent Li(2), and one Ni(1) atom.
CsLi7(NiO3)2 crystallizes in the monoclinic C2/m space group. Cs(1) is bonded in a 22-coordinate geometry to two equivalent Li(1), six equivalent Li(2), four equivalent Ni(1), four equivalent O(1), and six equivalent O(3) atoms. Both Cs(1)-Li(1) bond lengths are 3.18 Å. There are two shorter (3.01 Å) and four longer (3.14 Å) Cs(1)-Li(2) bond lengths. All Cs(1)-Ni(1) bond lengths are 3.38 Å. All Cs(1)-O(1) bond lengths are 3.40 Å. There are four shorter (3.08 Å) and two longer (3.17 Å) Cs(1)-O(3) bond lengths. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one Cs(1), one O(2), one O(3), and two equivalent O(1) atoms to form distorted LiCsO4 trigonal pyramids that share  a cornercorner with one Li(3)O4 tetrahedra, corners with three equivalent Li(2)Cs3O4 trigonal pyramids, corners with three equivalent Li(1)CsO4 trigonal pyramids, edges with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Li(2)Cs3O4 trigonal pyramid, and faces with two equivalent Li(2)Cs3O4 trigonal pyramids. The Li(1)-O(2) bond length is 2.12 Å. The Li(1)-O(3) bond length is 2.15 Å. Both Li(1)-O(1) bond lengths are 1.98 Å. In the second Li site, Li(2) is bonded to three equivalent Cs(1), one O(1), and three equivalent O(3) atoms to form distorted LiCs3O4 trigonal pyramids that share  a cornercorner with one Li(3)O4 tetrahedra, corners with three equivalent Li(1)CsO4 trigonal pyramids, corners with seven equivalent Li(2)Cs3O4 trigonal pyramids,  an edgeedge with one Li(1)CsO4 trigonal pyramid, edges with three equivalent Li(2)Cs3O4 trigonal pyramids, faces with two equivalent Li(2)Cs3O4 trigonal pyramids, and faces with two equivalent Li(1)CsO4 trigonal pyramids. The Li(2)-O(1) bond length is 2.16 Å. There are two shorter (1.97 Å) and one longer (2.26 Å) Li(2)-O(3) bond length. In the third Li site, Li(3) is bonded to one O(1) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra,  a cornercorner with one Li(2)Cs3O4 trigonal pyramid,  a cornercorner with one Li(1)CsO4 trigonal pyramid, edges with two equivalent Li(3)O4 tetrahedra, and edges with two equivalent Li(1)CsO4 trigonal pyramids. The Li(3)-O(1) bond length is 2.12 Å. There is one shorter (1.98 Å) and two longer (2.02 Å) Li(3)-O(2) bond lengths. In the fourth Li site, Li(4) is bonded in a linear geometry to two equivalent O(2) atoms. Both Li(4)-O(2) bond lengths are 1.92 Å. Ni(1) is bonded in a trigonal planar geometry to two equivalent Cs(1), one O(1), one O(2), and one O(3) atom. The Ni(1)-O(1) bond length is 1.86 Å. The Ni(1)-O(2) bond length is 1.87 Å. The Ni(1)-O(3) bond length is 1.86 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one Li(2), one Li(3), two equivalent Li(1), and one Ni(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(4), three equivalent Li(3), and one Ni(1) atom to form a mixture of distorted corner and edge-sharing OLi5Ni octahedra. The corner-sharing octahedral tilt angles range from 0-46°. In the third O site, O(3) is bonded in a 5-coordinate geometry to three equivalent Cs(1), one Li(1), three equivalent Li(2), and one Ni(1) atom.