Na3IrH6 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one H(4), two equivalent H(2), and four equivalent H(1) atoms. In the second Na site, Na(2) is bonded in a 10-coordinate geometry to one H(4), two equivalent H(1), three equivalent H(3), and four equivalent H(2) atoms. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one H(3), two equivalent H(1), two equivalent H(2), and two equivalent H(4) atoms. Ir(1) is bonded in an octahedral geometry to one H(3), one H(4), two equivalent H(1), and two equivalent H(2) atoms. There are four inequivalent H sites. In the first H site, H(4) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), two equivalent Na(3), and one Ir(1) atom. In the second H site, H(1) is bonded to one Na(2), one Na(3), two equivalent Na(1), and one Ir(1) atom to form a mixture of distorted edge, corner, and face-sharing HNa4Ir square pyramids. In the third H site, H(2) is bonded to one Na(1), one Na(3), two equivalent Na(2), and one Ir(1) atom to form a mixture of distorted edge, corner, and face-sharing HNa4Ir square pyramids. In the fourth H site, H(3) is bonded in a 5-coordinate geometry to one Na(3), three equivalent Na(2), and one Ir(1) atom.
Na3IrH6 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one H(4), two equivalent H(2), and four equivalent H(1) atoms. The Na(1)-H(4) bond length is 2.42 Å. Both Na(1)-H(2) bond lengths are 2.38 Å. There are two shorter (2.36 Å) and two longer (2.49 Å) Na(1)-H(1) bond lengths. In the second Na site, Na(2) is bonded in a 10-coordinate geometry to one H(4), two equivalent H(1), three equivalent H(3), and four equivalent H(2) atoms. The Na(2)-H(4) bond length is 2.20 Å. Both Na(2)-H(1) bond lengths are 2.62 Å. There is one shorter (2.24 Å) and two longer (2.61 Å) Na(2)-H(3) bond lengths. There are two shorter (2.37 Å) and two longer (2.59 Å) Na(2)-H(2) bond lengths. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one H(3), two equivalent H(1), two equivalent H(2), and two equivalent H(4) atoms. The Na(3)-H(3) bond length is 2.13 Å. Both Na(3)-H(1) bond lengths are 2.55 Å. Both Na(3)-H(2) bond lengths are 2.30 Å. Both Na(3)-H(4) bond lengths are 2.62 Å. Ir(1) is bonded in an octahedral geometry to one H(3), one H(4), two equivalent H(1), and two equivalent H(2) atoms. The Ir(1)-H(3) bond length is 1.66 Å. The Ir(1)-H(4) bond length is 1.67 Å. Both Ir(1)-H(1) bond lengths are 1.68 Å. Both Ir(1)-H(2) bond lengths are 1.67 Å. There are four inequivalent H sites. In the first H site, H(4) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), two equivalent Na(3), and one Ir(1) atom. In the second H site, H(1) is bonded to one Na(2), one Na(3), two equivalent Na(1), and one Ir(1) atom to form a mixture of distorted edge, corner, and face-sharing HNa4Ir square pyramids. In the third H site, H(2) is bonded to one Na(1), one Na(3), two equivalent Na(2), and one Ir(1) atom to form a mixture of distorted edge, corner, and face-sharing HNa4Ir square pyramids. In the fourth H site, H(3) is bonded in a 5-coordinate geometry to one Na(3), three equivalent Na(2), and one Ir(1) atom.