LiBa6Nb2Ir(O6Cl)2 crystallizes in the monoclinic Cm space group. Li(1) is bonded in a 3-coordinate geometry to one Ba(6), two equivalent O(3), and one Cl(1) atom. There are six inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 1-coordinate geometry to one O(6) and one Cl(2) atom. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one O(8), two equivalent O(1), two equivalent O(2), two equivalent O(4), and one Cl(2) atom. In the third Ba site, Ba(3) is bonded in a 3-coordinate geometry to one O(4), two equivalent O(2), and two equivalent Cl(2) atoms. In the fourth Ba site, Ba(4) is bonded in a 9-coordinate geometry to one O(7), two equivalent O(1), two equivalent O(2), two equivalent O(5), and two equivalent O(8) atoms. In the fifth Ba site, Ba(5) is bonded in a 9-coordinate geometry to one O(8), two equivalent O(1), two equivalent O(3), two equivalent O(5), and two equivalent O(7) atoms. In the sixth Ba site, Ba(6) is bonded in a 9-coordinate geometry to one Li(1), one O(7), two equivalent O(3), two equivalent O(5), two equivalent O(6), and one Cl(1) atom. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(4), one O(8), two equivalent O(1), and two equivalent O(2) atoms to form distorted NbO6 octahedra that share  a faceface with one Ir(1)O6 octahedra. In the second Nb site, Nb(2) is bonded to one O(6), one O(7), two equivalent O(3), and two equivalent O(5) atoms to form distorted NbO6 octahedra that share  a faceface with one Ir(1)O6 octahedra. Ir(1) is bonded to one O(7), one O(8), two equivalent O(1), and two equivalent O(5) atoms to form IrO6 octahedra that share  a faceface with one Nb(1)O6 octahedra and  a faceface with one Nb(2)O6 octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Ba(2), one Ba(4), one Ba(5), 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(2), one Ba(3), one Ba(4), and one Nb(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Li(1), one Ba(5), one Ba(6), and one Nb(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ba(3), two equivalent Ba(2), and one Nb(1) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Ba(4), one Ba(5), one Ba(6), one Nb(2), and one Ir(1) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Ba(1), two equivalent Ba(6), and one Nb(2) atom. In the seventh O site, O(7) is bonded to one Ba(4), one Ba(6), two equivalent Ba(5), one Nb(2), and one Ir(1) atom to form a mixture of distorted corner and edge-sharing OBa4NbIr octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the eighth O site, O(8) is bonded to one Ba(2), one Ba(5), two equivalent Ba(4), one Nb(1), and one Ir(1) atom to form a mixture of corner and edge-sharing OBa4NbIr octahedra. The corner-sharing octahedral tilt angles are 2°. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to one Li(1) and one Ba(6) atom. In the second Cl site, Cl(2) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(2), and two equivalent Ba(3) atoms.
LiBa6Nb2Ir(O6Cl)2 crystallizes in the monoclinic Cm space group. Li(1) is bonded in a 3-coordinate geometry to one Ba(6), two equivalent O(3), and one Cl(1) atom. The Li(1)-Ba(6) bond length is 2.69 Å. Both Li(1)-O(3) bond lengths are 1.80 Å. The Li(1)-Cl(1) bond length is 2.50 Å. There are six inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 1-coordinate geometry to one O(6) and one Cl(2) atom. The Ba(1)-O(6) bond length is 2.41 Å. The Ba(1)-Cl(2) bond length is 3.09 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one O(8), two equivalent O(1), two equivalent O(2), two equivalent O(4), and one Cl(2) atom. The Ba(2)-O(8) bond length is 2.74 Å. Both Ba(2)-O(1) bond lengths are 2.64 Å. Both Ba(2)-O(2) bond lengths are 2.87 Å. Both Ba(2)-O(4) bond lengths are 3.07 Å. The Ba(2)-Cl(2) bond length is 3.20 Å. In the third Ba site, Ba(3) is bonded in a 3-coordinate geometry to one O(4), two equivalent O(2), and two equivalent Cl(2) atoms. The Ba(3)-O(4) bond length is 2.58 Å. Both Ba(3)-O(2) bond lengths are 2.52 Å. Both Ba(3)-Cl(2) bond lengths are 3.51 Å. In the fourth Ba site, Ba(4) is bonded in a 9-coordinate geometry to one O(7), two equivalent O(1), two equivalent O(2), two equivalent O(5), and two equivalent O(8) atoms. The Ba(4)-O(7) bond length is 3.05 Å. Both Ba(4)-O(1) bond lengths are 2.82 Å. Both Ba(4)-O(2) bond lengths are 2.92 Å. Both Ba(4)-O(5) bond lengths are 3.16 Å. Both Ba(4)-O(8) bond lengths are 2.94 Å. In the fifth Ba site, Ba(5) is bonded in a 9-coordinate geometry to one O(8), two equivalent O(1), two equivalent O(3), two equivalent O(5), and two equivalent O(7) atoms. The Ba(5)-O(8) bond length is 2.87 Å. Both Ba(5)-O(1) bond lengths are 2.90 Å. Both Ba(5)-O(3) bond lengths are 3.31 Å. Both Ba(5)-O(5) bond lengths are 2.79 Å. Both Ba(5)-O(7) bond lengths are 2.96 Å. In the sixth Ba site, Ba(6) is bonded in a 9-coordinate geometry to one Li(1), one O(7), two equivalent O(3), two equivalent O(5), two equivalent O(6), and one Cl(1) atom. The Ba(6)-O(7) bond length is 2.47 Å. Both Ba(6)-O(3) bond lengths are 2.75 Å. Both Ba(6)-O(5) bond lengths are 2.61 Å. Both Ba(6)-O(6) bond lengths are 3.12 Å. The Ba(6)-Cl(1) bond length is 3.35 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(4), one O(8), two equivalent O(1), and two equivalent O(2) atoms to form distorted NbO6 octahedra that share  a faceface with one Ir(1)O6 octahedra. The Nb(1)-O(4) bond length is 1.90 Å. The Nb(1)-O(8) bond length is 2.31 Å. Both Nb(1)-O(1) bond lengths are 2.17 Å. Both Nb(1)-O(2) bond lengths are 1.93 Å. In the second Nb site, Nb(2) is bonded to one O(6), one O(7), two equivalent O(3), and two equivalent O(5) atoms to form distorted NbO6 octahedra that share  a faceface with one Ir(1)O6 octahedra. The Nb(2)-O(6) bond length is 1.89 Å. The Nb(2)-O(7) bond length is 2.29 Å. Both Nb(2)-O(3) bond lengths are 2.00 Å. Both Nb(2)-O(5) bond lengths are 2.11 Å. Ir(1) is bonded to one O(7), one O(8), two equivalent O(1), and two equivalent O(5) atoms to form IrO6 octahedra that share  a faceface with one Nb(1)O6 octahedra and  a faceface with one Nb(2)O6 octahedra. The Ir(1)-O(7) bond length is 2.09 Å. The Ir(1)-O(8) bond length is 2.10 Å. Both Ir(1)-O(1) bond lengths are 2.07 Å. Both Ir(1)-O(5) bond lengths are 2.09 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Ba(2), one Ba(4), one Ba(5), 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(2), one Ba(3), one Ba(4), and one Nb(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Li(1), one Ba(5), one Ba(6), and one Nb(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ba(3), two equivalent Ba(2), and one Nb(1) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Ba(4), one Ba(5), one Ba(6), one Nb(2), and one Ir(1) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Ba(1), two equivalent Ba(6), and one Nb(2) atom. In the seventh O site, O(7) is bonded to one Ba(4), one Ba(6), two equivalent Ba(5), one Nb(2), and one Ir(1) atom to form a mixture of distorted corner and edge-sharing OBa4NbIr octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the eighth O site, O(8) is bonded to one Ba(2), one Ba(5), two equivalent Ba(4), one Nb(1), and one Ir(1) atom to form a mixture of corner and edge-sharing OBa4NbIr octahedra. The corner-sharing octahedral tilt angles are 2°. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to one Li(1) and one Ba(6) atom. In the second Cl site, Cl(2) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(2), and two equivalent Ba(3) atoms.