NaIr3B4 crystallizes in the orthorhombic Aem2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 10-coordinate geometry to two equivalent Ir(1), two equivalent Ir(2), four equivalent Ir(5), and two equivalent B(1) atoms. In the second Na site, Na(2) is bonded in a 9-coordinate geometry to one Ir(2), two equivalent Ir(3), two equivalent Ir(4), two equivalent Ir(5), and two equivalent B(4) atoms. There are five inequivalent Ir sites. In the first Ir site, Ir(1) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent B(1), two equivalent B(2), and two equivalent B(4) atoms. In the second Ir site, Ir(2) is bonded in a 7-coordinate geometry to one Na(2), two equivalent Na(1), two equivalent B(1), two equivalent B(2), and two equivalent B(3) atoms. In the third Ir site, Ir(3) is bonded in a 4-coordinate geometry to two equivalent Na(2), two equivalent B(3), and two equivalent B(4) atoms. In the fourth Ir site, Ir(4) is bonded in a 8-coordinate geometry to two equivalent Na(2), two equivalent B(1), two equivalent B(3), and two equivalent B(4) atoms. In the fifth Ir site, Ir(5) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), one B(3), one B(4), and two equivalent B(2) atoms. There are four inequivalent B sites. In the first B site, B(1) is bonded in a 7-coordinate geometry to one Na(1), one Ir(1), one Ir(2), one Ir(4), one B(1), one B(3), and one B(4) atom. In the second B site, B(2) is bonded in a distorted pentagonal planar geometry to one Ir(1), one Ir(2), two equivalent Ir(5), and one B(2) atom. In the third B site, B(3) is bonded in a distorted pentagonal planar geometry to one Ir(2), one Ir(3), one Ir(4), one Ir(5), and one B(1) atom. In the fourth B site, B(4) is bonded in a 5-coordinate geometry to one Na(2), one Ir(1), one Ir(3), one Ir(4), one Ir(5), and one B(1) atom.
NaIr3B4 crystallizes in the orthorhombic Aem2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 10-coordinate geometry to two equivalent Ir(1), two equivalent Ir(2), four equivalent Ir(5), and two equivalent B(1) atoms. Both Na(1)-Ir(1) bond lengths are 3.35 Å. Both Na(1)-Ir(2) bond lengths are 3.34 Å. There are two shorter (3.15 Å) and two longer (3.18 Å) Na(1)-Ir(5) bond lengths. Both Na(1)-B(1) bond lengths are 2.99 Å. In the second Na site, Na(2) is bonded in a 9-coordinate geometry to one Ir(2), two equivalent Ir(3), two equivalent Ir(4), two equivalent Ir(5), and two equivalent B(4) atoms. The Na(2)-Ir(2) bond length is 3.10 Å. Both Na(2)-Ir(3) bond lengths are 3.19 Å. Both Na(2)-Ir(4) bond lengths are 3.08 Å. Both Na(2)-Ir(5) bond lengths are 3.30 Å. Both Na(2)-B(4) bond lengths are 3.12 Å. There are five inequivalent Ir sites. In the first Ir site, Ir(1) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent B(1), two equivalent B(2), and two equivalent B(4) atoms. Both Ir(1)-B(1) bond lengths are 2.13 Å. Both Ir(1)-B(2) bond lengths are 2.18 Å. Both Ir(1)-B(4) bond lengths are 2.11 Å. In the second Ir site, Ir(2) is bonded in a 7-coordinate geometry to one Na(2), two equivalent Na(1), two equivalent B(1), two equivalent B(2), and two equivalent B(3) atoms. Both Ir(2)-B(1) bond lengths are 2.13 Å. Both Ir(2)-B(2) bond lengths are 2.19 Å. Both Ir(2)-B(3) bond lengths are 2.11 Å. In the third Ir site, Ir(3) is bonded in a 4-coordinate geometry to two equivalent Na(2), two equivalent B(3), and two equivalent B(4) atoms. Both Ir(3)-B(3) bond lengths are 2.04 Å. Both Ir(3)-B(4) bond lengths are 2.04 Å. In the fourth Ir site, Ir(4) is bonded in a 8-coordinate geometry to two equivalent Na(2), two equivalent B(1), two equivalent B(3), and two equivalent B(4) atoms. Both Ir(4)-B(1) bond lengths are 2.19 Å. Both Ir(4)-B(3) bond lengths are 2.19 Å. Both Ir(4)-B(4) bond lengths are 2.20 Å. In the fifth Ir site, Ir(5) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), one B(3), one B(4), and two equivalent B(2) atoms. The Ir(5)-B(3) bond length is 2.09 Å. The Ir(5)-B(4) bond length is 2.09 Å. Both Ir(5)-B(2) bond lengths are 2.10 Å. There are four inequivalent B sites. In the first B site, B(1) is bonded in a 7-coordinate geometry to one Na(1), one Ir(1), one Ir(2), one Ir(4), one B(1), one B(3), and one B(4) atom. The B(1)-B(1) bond length is 1.92 Å. The B(1)-B(3) bond length is 1.72 Å. The B(1)-B(4) bond length is 1.73 Å. In the second B site, B(2) is bonded in a distorted pentagonal planar geometry to one Ir(1), one Ir(2), two equivalent Ir(5), and one B(2) atom. The B(2)-B(2) bond length is 1.78 Å. In the third B site, B(3) is bonded in a distorted pentagonal planar geometry to one Ir(2), one Ir(3), one Ir(4), one Ir(5), and one B(1) atom. In the fourth B site, B(4) is bonded in a 5-coordinate geometry to one Na(2), one Ir(1), one Ir(3), one Ir(4), one Ir(5), and one B(1) atom.