Na3IrN2 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. In the second Na site, Na(2) is bonded in a distorted L-shaped geometry to two equivalent N(1) atoms. In the third Na site, Na(3) is bonded in a 1-coordinate geometry to one N(1) and two equivalent N(2) atoms. Ir(1) is bonded in a distorted bent 150 degrees geometry to one N(1) and one N(2) atom. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Ir(1) atom to form distorted edge-sharing NNa5Ir octahedra. In the second N site, N(2) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Na(3), one Ir(1), and one N(2) atom.
Na3IrN2 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. There is one shorter (2.36 Å) and one longer (2.38 Å) Na(1)-N(1) bond length. There is one shorter (2.44 Å) and one longer (2.53 Å) Na(1)-N(2) bond length. In the second Na site, Na(2) is bonded in a distorted L-shaped geometry to two equivalent N(1) atoms. There is one shorter (2.53 Å) and one longer (2.62 Å) Na(2)-N(1) bond length. In the third Na site, Na(3) is bonded in a 1-coordinate geometry to one N(1) and two equivalent N(2) atoms. The Na(3)-N(1) bond length is 2.50 Å. There is one shorter (2.77 Å) and one longer (2.88 Å) Na(3)-N(2) bond length. Ir(1) is bonded in a distorted bent 150 degrees geometry to one N(1) and one N(2) atom. The Ir(1)-N(1) bond length is 1.80 Å. The Ir(1)-N(2) bond length is 1.92 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Ir(1) atom to form distorted edge-sharing NNa5Ir octahedra. In the second N site, N(2) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Na(3), one Ir(1), and one N(2) atom. The N(2)-N(2) bond length is 1.23 Å.