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CeOs2 is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Ce3+ is bonded in a 12-coordinate geometry to twelve equivalent Os+1.50- atoms. All Ce–Os bond lengths are 3.16 Å. Os+1.50- is bonded to six equivalent Ce3+ and six equivalent Os+1.50- atoms to form a mixture of corner, edge, and face-sharing OsCe6Os6 cuboctahedra. All Os–Os bond lengths are 2.70 Å.
CeOs2 is Hexagonal Laves structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Ce3+ is bonded in a 12-coordinate geometry to twelve Os+1.50- atoms. There are a spread of Ce–Os bond distances ranging from 3.12–3.24 Å. There are two inequivalent Os+1.50- sites. In the first Os+1.50- site, Os+1.50- is bonded to six equivalent Ce3+ and six equivalent Os+1.50- atoms to form a mixture of face, edge, and corner-sharing OsCe6Os6 cuboctahedra. All Os–Os bond lengths are 2.74 Å. In the second Os+1.50- site, Os+1.50- is bonded to six equivalent Ce3+ and six Os+1.50- atoms to form a mixture of face, edge, and corner-sharing OsCe6Os6 cuboctahedra. There are two shorter (2.62 Å) and two longer (2.74 Å) Os–Os bond lengths.