Ba4Ir3O10 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to one O(2), two equivalent O(1), two equivalent O(3), two equivalent O(4), and three equivalent O(5) atoms. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one O(1), one O(5), two equivalent O(3), two equivalent O(4), and three equivalent O(2) atoms. There are two inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form face-sharing IrO6 octahedra. In the second Ir site, Ir(2) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form a mixture of face and corner-sharing IrO6 octahedra. The corner-sharing octahedral tilt angles are 24°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Ba(2), two equivalent Ba(1), and two equivalent Ir(2) atoms. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Ba(1), three equivalent Ba(2), and one Ir(2) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), one Ir(1), and one Ir(2) atom. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), one Ir(1), and one Ir(2) atom. In the fifth O site, O(5) is bonded to one Ba(2), three equivalent Ba(1), one Ir(1), and one Ir(2) atom to form a mixture of distorted edge and corner-sharing OBa4Ir2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°.
Ba4Ir3O10 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to one O(2), two equivalent O(1), two equivalent O(3), two equivalent O(4), and three equivalent O(5) atoms. The Ba(1)-O(2) bond length is 2.62 Å. There is one shorter (2.68 Å) and one longer (3.31 Å) Ba(1)-O(1) bond length. There is one shorter (2.80 Å) and one longer (2.95 Å) Ba(1)-O(3) bond length. There is one shorter (2.81 Å) and one longer (2.99 Å) Ba(1)-O(4) bond length. There are a spread of Ba(1)-O(5) bond distances ranging from 2.80-2.95 Å. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one O(1), one O(5), two equivalent O(3), two equivalent O(4), and three equivalent O(2) atoms. The Ba(2)-O(1) bond length is 2.70 Å. The Ba(2)-O(5) bond length is 2.82 Å. There is one shorter (2.69 Å) and one longer (3.06 Å) Ba(2)-O(3) bond length. There is one shorter (2.80 Å) and one longer (2.85 Å) Ba(2)-O(4) bond length. There are a spread of Ba(2)-O(2) bond distances ranging from 2.95-3.13 Å. There are two inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form face-sharing IrO6 octahedra. Both Ir(1)-O(3) bond lengths are 2.06 Å. Both Ir(1)-O(4) bond lengths are 2.05 Å. Both Ir(1)-O(5) bond lengths are 2.05 Å. In the second Ir site, Ir(2) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form a mixture of face and corner-sharing IrO6 octahedra. The corner-sharing octahedral tilt angles are 24°. The Ir(2)-O(2) bond length is 1.95 Å. The Ir(2)-O(3) bond length is 2.06 Å. The Ir(2)-O(4) bond length is 2.07 Å. The Ir(2)-O(5) bond length is 2.13 Å. There is one shorter (1.99 Å) and one longer (2.02 Å) Ir(2)-O(1) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Ba(2), two equivalent Ba(1), and two equivalent Ir(2) atoms. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Ba(1), three equivalent Ba(2), and one Ir(2) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), one Ir(1), and one Ir(2) atom. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), one Ir(1), and one Ir(2) atom. In the fifth O site, O(5) is bonded to one Ba(2), three equivalent Ba(1), one Ir(1), and one Ir(2) atom to form a mixture of distorted edge and corner-sharing OBa4Ir2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°.