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Na2Cl is trigonal omega-like structured and crystallizes in the trigonal R-3m space group. The structure is two-dimensional and consists of three Na2Cl sheets oriented in the (0, 0, 1) direction. Na is bonded in a distorted T-shaped geometry to three equivalent Cl atoms. All Na–Cl bond lengths are 2.84 Å. Cl is bonded to six equivalent Na atoms to form edge-sharing ClNa6 octahedra.
Na2Cl crystallizes in the orthorhombic Cmmm space group. The structure is two-dimensional and consists of two Na2Cl sheets oriented in the (1, 0, 0) direction. there are three inequivalent Na sites. In the first Na site, Na is bonded in a 8-coordinate geometry to four equivalent Na atoms. All Na–Na bond lengths are 3.29 Å. In the second Na site, Na is bonded in a square co-planar geometry to four equivalent Cl atoms. All Na–Cl bond lengths are 2.92 Å. In the third Na site, Na is bonded in an L-shaped geometry to two equivalent Na and two equivalent Cl atoms. Both Na–Cl bond lengths are 2.78 Å. Cl is bonded in a rectangular see-saw-like geometry to four Na atoms.