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NaAg2 is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Na is bonded in a 12-coordinate geometry to twelve equivalent Ag atoms. All Na–Ag bond lengths are 3.34 Å. Ag is bonded to six equivalent Na and six equivalent Ag atoms to form a mixture of edge, face, and corner-sharing AgNa6Ag6 cuboctahedra. All Ag–Ag bond lengths are 2.85 Å.
NaAg3 is Uranium Silicide-like structured and crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. Na is bonded to twelve Ag atoms to form a mixture of corner, edge, and face-sharing NaAg12 cuboctahedra. There are four shorter (3.00 Å) and eight longer (3.02 Å) Na–Ag bond lengths. There are two inequivalent Ag sites. In the first Ag site, Ag is bonded to four equivalent Na atoms to form a mixture of distorted corner and edge-sharing AgNa4 cuboctahedra. In the second Ag site, Ag is bonded in a distorted square co-planar geometry to four equivalent Na atoms.