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NaAg2Sn crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two NaAg2Sn ribbons oriented in the (0, 1, 0) direction. Na is bonded in a linear geometry to two equivalent Ag atoms. Both Na–Ag bond lengths are 3.02 Å. Ag is bonded in a linear geometry to one Na and one Sn atom. The Ag–Sn bond length is 2.76 Å. Sn is bonded in a linear geometry to two equivalent Ag atoms.
NaAg2Sn is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Na is bonded in a distorted body-centered cubic geometry to eight equivalent Ag and six equivalent Sn atoms. All Na–Ag bond lengths are 3.01 Å. All Na–Sn bond lengths are 3.47 Å. Ag is bonded in a distorted body-centered cubic geometry to four equivalent Na and four equivalent Sn atoms. All Ag–Sn bond lengths are 3.01 Å. Sn is bonded in a 8-coordinate geometry to six equivalent Na and eight equivalent Ag atoms.