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Na3Rh crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Na is bonded in a distorted see-saw-like geometry to four equivalent Rh atoms. There are two shorter (3.12 Å) and two longer (3.18 Å) Na–Rh bond lengths. Rh is bonded to twelve equivalent Na atoms to form a mixture of face and corner-sharing RhNa12 cuboctahedra.
Na3Rh crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are three inequivalent Na sites. In the first Na site, Na is bonded in a distorted bent 120 degrees geometry to two equivalent Rh atoms. There are one shorter (2.92 Å) and one longer (3.01 Å) Na–Rh bond lengths. In the second Na site, Na is bonded in a distorted trigonal planar geometry to three equivalent Rh atoms. There are one shorter (2.94 Å) and two longer (2.98 Å) Na–Rh bond lengths. In the third Na site, Na is bonded in a distorted trigonal planar geometry to three equivalent Rh atoms. There are one shorter (3.02 Å) and two longer (3.03 Å) Na–Rh bond lengths. Rh is bonded in a 8-coordinate geometry to eight Na atoms.