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Na2AuHg crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two Na2AuHg ribbons oriented in the (1, 0, 0) direction. Na is bonded in a linear geometry to one Au and one Hg atom. The Na–Au bond length is 2.79 Å. The Na–Hg bond length is 3.13 Å. Au is bonded in a linear geometry to two equivalent Na atoms. Hg is bonded in a linear geometry to two equivalent Na atoms.
Na2AuHg is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Na is bonded in a body-centered cubic geometry to four equivalent Au and four equivalent Hg atoms. All Na–Au bond lengths are 3.15 Å. All Na–Hg bond lengths are 3.15 Å. Au is bonded in a body-centered cubic geometry to eight equivalent Na atoms. Hg is bonded in a body-centered cubic geometry to eight equivalent Na atoms.