Ba6CaNb2Ir(O6Cl)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), and three equivalent Cl(1) atoms. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), two equivalent O(4), and one Cl(1) atom. In the third Ba site, Ba(3) is bonded in a 8-coordinate geometry to one Ir(1), one O(1), one O(2), one O(3), one O(4), one O(5), and two equivalent O(6) atoms. Ca(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form distorted CaO6 octahedra that share corners with six equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. Nb(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form NbO6 octahedra that share corners with three equivalent Ca(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. Ir(1) is bonded in a distorted square co-planar geometry to two equivalent Ba(3), two equivalent O(1), and two equivalent O(5) atoms. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Ba(2), one Ba(3), one Ca(1), one Nb(1), and one Ir(1) atom. In the second O site, O(2) is bonded in a 1-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), and one Nb(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), and one Nb(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(3), two equivalent Ba(2), and one Nb(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Ba(2), one Ba(3), one Ca(1), one Nb(1), and one Ir(1) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Ba(2), two equivalent Ba(3), one Ca(1), and one Nb(1) atom. Cl(1) is bonded in a distorted see-saw-like geometry to one Ba(2) and three equivalent Ba(1) atoms.
Ba6CaNb2Ir(O6Cl)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), and three equivalent Cl(1) atoms. The Ba(1)-O(2) bond length is 2.60 Å. The Ba(1)-O(3) bond length is 2.60 Å. The Ba(1)-O(4) bond length is 2.61 Å. There are a spread of Ba(1)-Cl(1) bond distances ranging from 3.21-3.40 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), two equivalent O(4), and one Cl(1) atom. The Ba(2)-O(1) bond length is 2.89 Å. The Ba(2)-O(2) bond length is 2.89 Å. The Ba(2)-O(3) bond length is 2.81 Å. The Ba(2)-O(5) bond length is 2.90 Å. The Ba(2)-O(6) bond length is 2.64 Å. There is one shorter (2.92 Å) and one longer (3.06 Å) Ba(2)-O(4) bond length. The Ba(2)-Cl(1) bond length is 3.12 Å. In the third Ba site, Ba(3) is bonded in a 8-coordinate geometry to one Ir(1), one O(1), one O(2), one O(3), one O(4), one O(5), and two equivalent O(6) atoms. The Ba(3)-Ir(1) bond length is 3.04 Å. The Ba(3)-O(1) bond length is 2.95 Å. The Ba(3)-O(2) bond length is 2.80 Å. The Ba(3)-O(3) bond length is 2.73 Å. The Ba(3)-O(4) bond length is 2.75 Å. The Ba(3)-O(5) bond length is 2.95 Å. There is one shorter (2.93 Å) and one longer (3.05 Å) Ba(3)-O(6) bond length. Ca(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form distorted CaO6 octahedra that share corners with six equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. Both Ca(1)-O(1) bond lengths are 2.27 Å. Both Ca(1)-O(5) bond lengths are 2.28 Å. Both Ca(1)-O(6) bond lengths are 2.93 Å. Nb(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form NbO6 octahedra that share corners with three equivalent Ca(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. The Nb(1)-O(1) bond length is 2.15 Å. The Nb(1)-O(2) bond length is 1.91 Å. The Nb(1)-O(3) bond length is 1.93 Å. The Nb(1)-O(4) bond length is 2.06 Å. The Nb(1)-O(5) bond length is 2.24 Å. The Nb(1)-O(6) bond length is 2.02 Å. Ir(1) is bonded in a distorted square co-planar geometry to two equivalent Ba(3), two equivalent O(1), and two equivalent O(5) atoms. Both Ir(1)-O(1) bond lengths are 2.12 Å. Both Ir(1)-O(5) bond lengths are 2.02 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Ba(2), one Ba(3), one Ca(1), one Nb(1), and one Ir(1) atom. In the second O site, O(2) is bonded in a 1-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), and one Nb(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), and one Nb(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(3), two equivalent Ba(2), and one Nb(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Ba(2), one Ba(3), one Ca(1), one Nb(1), and one Ir(1) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Ba(2), two equivalent Ba(3), one Ca(1), and one Nb(1) atom. Cl(1) is bonded in a distorted see-saw-like geometry to one Ba(2) and three equivalent Ba(1) atoms.