Na3IrN2S2(O5Cl2)2 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one Cl(1), and two equivalent Cl(2) atoms. In the second Na site, Na(2) is bonded to two equivalent O(3), two equivalent Cl(1), and two equivalent Cl(2) atoms to form distorted NaCl4O2 octahedra that share edges with two equivalent Ir(1)S2Cl4 octahedra. Ir(1) is bonded to two equivalent S(1), two equivalent Cl(1), and two equivalent Cl(2) atoms to form IrS2Cl4 octahedra that share edges with two equivalent Na(2)Cl4O2 octahedra. N(1) is bonded in a bent 120 degrees geometry to one O(4) and one O(5) atom. S(1) is bonded in a distorted trigonal non-coplanar geometry to one Ir(1), one O(1), one O(2), and one O(3) atom. There are five inequivalent O sites. In the first O site, O(3) is bonded in a bent 120 degrees geometry to one Na(2) and one S(1) atom. In the second O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one N(1) atom. In the third O site, O(5) is bonded in a single-bond geometry to one N(1) atom. In the fourth O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one S(1) atom. In the fifth O site, O(2) is bonded in a bent 150 degrees geometry to one Na(1) and one S(1) atom. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a T-shaped geometry to one Na(1), one Na(2), and one Ir(1) atom. In the second Cl site, Cl(2) is bonded to one Na(2), two equivalent Na(1), and one Ir(1) atom to form corner-sharing ClNa3Ir tetrahedra.
Na3IrN2S2(O5Cl2)2 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one Cl(1), and two equivalent Cl(2) atoms. The Na(1)-O(1) bond length is 2.39 Å. The Na(1)-O(2) bond length is 2.32 Å. The Na(1)-O(4) bond length is 2.83 Å. The Na(1)-Cl(1) bond length is 2.96 Å. There is one shorter (2.81 Å) and one longer (2.84 Å) Na(1)-Cl(2) bond length. In the second Na site, Na(2) is bonded to two equivalent O(3), two equivalent Cl(1), and two equivalent Cl(2) atoms to form distorted NaCl4O2 octahedra that share edges with two equivalent Ir(1)S2Cl4 octahedra. Both Na(2)-O(3) bond lengths are 2.32 Å. Both Na(2)-Cl(1) bond lengths are 2.82 Å. Both Na(2)-Cl(2) bond lengths are 2.80 Å. Ir(1) is bonded to two equivalent S(1), two equivalent Cl(1), and two equivalent Cl(2) atoms to form IrS2Cl4 octahedra that share edges with two equivalent Na(2)Cl4O2 octahedra. Both Ir(1)-S(1) bond lengths are 2.55 Å. Both Ir(1)-Cl(1) bond lengths are 2.32 Å. Both Ir(1)-Cl(2) bond lengths are 2.37 Å. N(1) is bonded in a bent 120 degrees geometry to one O(4) and one O(5) atom. The N(1)-O(4) bond length is 1.22 Å. The N(1)-O(5) bond length is 1.21 Å. S(1) is bonded in a distorted trigonal non-coplanar geometry to one Ir(1), one O(1), one O(2), and one O(3) atom. The S(1)-O(1) bond length is 1.47 Å. The S(1)-O(2) bond length is 1.47 Å. The S(1)-O(3) bond length is 1.47 Å. There are five inequivalent O sites. In the first O site, O(3) is bonded in a bent 120 degrees geometry to one Na(2) and one S(1) atom. In the second O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one N(1) atom. In the third O site, O(5) is bonded in a single-bond geometry to one N(1) atom. In the fourth O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one S(1) atom. In the fifth O site, O(2) is bonded in a bent 150 degrees geometry to one Na(1) and one S(1) atom. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a T-shaped geometry to one Na(1), one Na(2), and one Ir(1) atom. In the second Cl site, Cl(2) is bonded to one Na(2), two equivalent Na(1), and one Ir(1) atom to form corner-sharing ClNa3Ir tetrahedra.