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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.
(Na(NO2)2)3Rh crystallizes in the trigonal R-3m space group. The structure is three-dimensional and consists of three rhodium molecules and one Na(NO2)2 framework. In the Na(NO2)2 framework, there are two inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded to six O2- atoms to form a mixture of corner and face-sharing NaO6 octahedra. There are three shorter (2.36 Å) and three longer (2.41 Å) Na–O bond lengths. In the second Na1+ site, Na1+ is bonded to twelve O2- atoms to form a mixture of corner and face-sharing NaO12 cuboctahedra. The corner-sharing octahedral tilt angles are 45°. There are six shorter (2.66 Å) and six longer (2.95 Å) Na–O bond lengths. N3+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.24 Å) and one longer (1.25 Å) N–O bond length. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a 3-coordinate geometry to two Na1+ and one N3+ atom. In the second O2- site, O2- is bonded in a 2-coordinate geometry to two Na1+ and one N3+ atom.