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GdCu is Tetraauricupride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Gd is bonded in a body-centered cubic geometry to eight equivalent Cu atoms. All Gd–Cu bond lengths are 3.04 Å. Cu is bonded in a body-centered cubic geometry to eight equivalent Gd atoms.
GdCu5 crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Gd is bonded in a 6-coordinate geometry to eighteen Cu atoms. There are six shorter (2.89 Å) and twelve longer (3.23 Å) Gd–Cu bond lengths. There are two inequivalent Cu sites. In the first Cu site, Cu is bonded to four equivalent Gd and eight Cu atoms to form a mixture of face, edge, and corner-sharing CuGd4Cu8 cuboctahedra. All Cu–Cu bond lengths are 2.50 Å. In the second Cu site, Cu is bonded in a 12-coordinate geometry to three equivalent Gd and six equivalent Cu atoms.