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CeCu2 crystallizes in the orthorhombic Imma space group. The structure is three-dimensional. Ce is bonded in a 12-coordinate geometry to twelve equivalent Cu atoms. There are a spread of Ce–Cu bond distances ranging from 2.99–3.09 Å. Cu is bonded in a 10-coordinate geometry to six equivalent Ce and four equivalent Cu atoms. There are a spread of Cu–Cu bond distances ranging from 2.54–2.85 Å.
CeCu2(Si0.5Ge0.5)2 crystallizes in the tetragonal I4mm space group. The structure is three-dimensional. Ce is bonded in a 12-coordinate geometry to eight equivalent Cu, four equivalent Ge, and four equivalent Si atoms. There are four shorter (3.19 Å) and four longer (3.29 Å) Ce–Cu bond lengths. All Ce–Ge bond lengths are 3.16 Å. All Ce–Si bond lengths are 3.17 Å. Cu is bonded in a 12-coordinate geometry to four equivalent Ce, four equivalent Cu, two equivalent Ge, and two equivalent Si atoms. All Cu–Cu bond lengths are 2.92 Å. Both Cu–Ge bond lengths are 2.47 Å. Both Cu–Si bond lengths are 2.39 Å. Ge is bonded in a 9-coordinate geometry to four equivalent Ce, four equivalent Cu, and one Si atom. The Ge–Si bond length is 2.43 Å. Si is bonded in a 1-coordinate geometry to four equivalent Ce, four equivalent Cu, and one Ge atom.