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CeNi2 is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Ce is bonded in a 12-coordinate geometry to twelve equivalent Ni atoms. All Ce–Ni bond lengths are 2.97 Å. Ni is bonded to six equivalent Ce and six equivalent Ni atoms to form a mixture of edge, corner, and face-sharing NiCe6Ni6 cuboctahedra. All Ni–Ni bond lengths are 2.54 Å.
CeNi5 crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Ce is bonded in a distorted hexagonal planar geometry to eighteen Ni atoms. There are six shorter (2.81 Å) and twelve longer (3.15 Å) Ce–Ni bond lengths. There are two inequivalent Ni sites. In the first Ni site, Ni is bonded to four equivalent Ce and eight Ni atoms to form a mixture of face, edge, and corner-sharing NiCe4Ni8 cuboctahedra. There are four shorter (2.43 Å) and four longer (2.44 Å) Ni–Ni bond lengths. In the second Ni site, Ni is bonded in a 12-coordinate geometry to three equivalent Ce and nine Ni atoms. All Ni–Ni bond lengths are 2.81 Å.
CeNi3 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are two inequivalent Ce sites. In the first Ce site, Ce is bonded in a 12-coordinate geometry to twelve Ni atoms. There are a spread of Ce–Ni bond distances ranging from 2.84–3.13 Å. In the second Ce site, Ce is bonded in a distorted hexagonal planar geometry to eighteen Ni atoms. There are six shorter (2.85 Å) and twelve longer (3.20 Å) Ce–Ni bond lengths. There are four inequivalent Ni sites. In the first Ni site, Ni is bonded to five Ce and seven Ni atoms to form distorted NiCe5Ni7 cuboctahedra that share corners with seventeen NiCe6Ni6 cuboctahedra, edges with eight equivalent NiCe5Ni7 cuboctahedra, and faces with fourteen NiCe5Ni7 cuboctahedra. There are a spread of Ni–Ni bond distances ranging from 2.46–2.53 Å. In the second Ni site, Ni is bonded to six equivalent Ce and six equivalent Ni atoms to form NiCe6Ni6 cuboctahedra that share corners with twelve equivalent NiCe5Ni7 cuboctahedra, edges with six equivalent NiCe6Ni6 cuboctahedra, and faces with eighteen equivalent NiCe5Ni7 cuboctahedra. In the third Ni site, Ni is bonded in a 12-coordinate geometry to three equivalent Ce and nine Ni atoms. All Ni–Ni bond lengths are 2.85 Å. In the fourth Ni site, Ni is bonded in a 12-coordinate geometry to three equivalent Ce and nine Ni atoms.