LiBa6Nb2Ir(O6Cl)2 crystallizes in the trigonal P3m1 space group. Li(1) is bonded in a distorted trigonal planar geometry to one Ba(4), one Ba(6), and three equivalent O(4) atoms. There are six inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 7-coordinate geometry to three equivalent O(3), one Cl(2), and three equivalent Cl(1) atoms. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to three equivalent O(1), six equivalent O(2), and one Cl(2) atom. In the third Ba site, Ba(3) is bonded in a 7-coordinate geometry to three equivalent O(2), one Cl(1), and three equivalent Cl(2) atoms. In the fourth Ba site, Ba(4) is bonded in a 10-coordinate geometry to one Li(1), three equivalent O(2), and six equivalent O(1) atoms. In the fifth Ba site, Ba(5) is bonded to three equivalent O(1), three equivalent O(3), and six equivalent O(4) atoms to form distorted BaO12 cuboctahedra that share corners with six equivalent Ba(5)O12 cuboctahedra, corners with three equivalent Nb(1)O6 octahedra, faces with three equivalent Nb(2)O6 octahedra, and faces with three equivalent Ir(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. In the sixth Ba site, Ba(6) is bonded in a 11-coordinate geometry to one Li(1), three equivalent O(4), six equivalent O(3), and one Cl(1) atom. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form NbO6 octahedra that share corners with three equivalent Ba(5)O12 cuboctahedra and  a faceface with one Ir(1)O6 octahedra. In the second Nb site, Nb(2) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form NbO6 octahedra that share faces with three equivalent Ba(5)O12 cuboctahedra and  a faceface with one Ir(1)O6 octahedra. Ir(1) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form IrO6 octahedra that share faces with three equivalent Ba(5)O12 cuboctahedra,  a faceface with one Nb(1)O6 octahedra, and  a faceface with one Nb(2)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Ba(2), one Ba(5), two equivalent Ba(4), one Nb(1), and one Ir(1) atom to form distorted OBa4NbIr octahedra that share corners with six equivalent O(1)Ba4NbIr octahedra,  a cornercorner with one Cl(2)Ba5 trigonal bipyramid, and faces with four equivalent O(1)Ba4NbIr octahedra. The corner-sharing octahedral tilt angles range from 14-61°. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Ba(3), one Ba(4), two equivalent Ba(2), and one Nb(1) atom. In the third O site, O(3) is bonded in a 1-coordinate geometry to one Ba(1), one Ba(5), two equivalent Ba(6), and one Nb(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Ba(6), two equivalent Ba(5), one Nb(2), and one Ir(1) atom. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to one Ba(3), one Ba(6), and three equivalent Ba(1) atoms. In the second Cl site, Cl(2) is bonded to one Ba(1), one Ba(2), and three equivalent Ba(3) atoms to form distorted ClBa5 trigonal bipyramids that share corners with three equivalent O(1)Ba4NbIr octahedra and corners with six equivalent Cl(2)Ba5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 44°.
LiBa6Nb2Ir(O6Cl)2 crystallizes in the trigonal P3m1 space group. Li(1) is bonded in a distorted trigonal planar geometry to one Ba(4), one Ba(6), and three equivalent O(4) atoms. The Li(1)-Ba(4) bond length is 2.68 Å. The Li(1)-Ba(6) bond length is 2.64 Å. All Li(1)-O(4) bond lengths are 1.85 Å. There are six inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 7-coordinate geometry to three equivalent O(3), one Cl(2), and three equivalent Cl(1) atoms. All Ba(1)-O(3) bond lengths are 2.55 Å. The Ba(1)-Cl(2) bond length is 3.38 Å. All Ba(1)-Cl(1) bond lengths are 3.59 Å. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to three equivalent O(1), six equivalent O(2), and one Cl(2) atom. All Ba(2)-O(1) bond lengths are 2.68 Å. All Ba(2)-O(2) bond lengths are 3.02 Å. The Ba(2)-Cl(2) bond length is 3.24 Å. In the third Ba site, Ba(3) is bonded in a 7-coordinate geometry to three equivalent O(2), one Cl(1), and three equivalent Cl(2) atoms. All Ba(3)-O(2) bond lengths are 2.58 Å. The Ba(3)-Cl(1) bond length is 3.22 Å. All Ba(3)-Cl(2) bond lengths are 3.54 Å. In the fourth Ba site, Ba(4) is bonded in a 10-coordinate geometry to one Li(1), three equivalent O(2), and six equivalent O(1) atoms. All Ba(4)-O(2) bond lengths are 2.71 Å. All Ba(4)-O(1) bond lengths are 3.00 Å. In the fifth Ba site, Ba(5) is bonded to three equivalent O(1), three equivalent O(3), and six equivalent O(4) atoms to form distorted BaO12 cuboctahedra that share corners with six equivalent Ba(5)O12 cuboctahedra, corners with three equivalent Nb(1)O6 octahedra, faces with three equivalent Nb(2)O6 octahedra, and faces with three equivalent Ir(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. All Ba(5)-O(1) bond lengths are 3.03 Å. All Ba(5)-O(3) bond lengths are 3.30 Å. All Ba(5)-O(4) bond lengths are 3.00 Å. In the sixth Ba site, Ba(6) is bonded in a 11-coordinate geometry to one Li(1), three equivalent O(4), six equivalent O(3), and one Cl(1) atom. All Ba(6)-O(4) bond lengths are 2.88 Å. All Ba(6)-O(3) bond lengths are 2.99 Å. The Ba(6)-Cl(1) bond length is 3.05 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form NbO6 octahedra that share corners with three equivalent Ba(5)O12 cuboctahedra and  a faceface with one Ir(1)O6 octahedra. All Nb(1)-O(1) bond lengths are 2.16 Å. All Nb(1)-O(2) bond lengths are 1.93 Å. In the second Nb site, Nb(2) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form NbO6 octahedra that share faces with three equivalent Ba(5)O12 cuboctahedra and  a faceface with one Ir(1)O6 octahedra. All Nb(2)-O(3) bond lengths are 1.92 Å. All Nb(2)-O(4) bond lengths are 2.20 Å. Ir(1) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form IrO6 octahedra that share faces with three equivalent Ba(5)O12 cuboctahedra,  a faceface with one Nb(1)O6 octahedra, and  a faceface with one Nb(2)O6 octahedra. All Ir(1)-O(1) bond lengths are 2.08 Å. All Ir(1)-O(4) bond lengths are 2.12 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Ba(2), one Ba(5), two equivalent Ba(4), one Nb(1), and one Ir(1) atom to form distorted OBa4NbIr octahedra that share corners with six equivalent O(1)Ba4NbIr octahedra,  a cornercorner with one Cl(2)Ba5 trigonal bipyramid, and faces with four equivalent O(1)Ba4NbIr octahedra. The corner-sharing octahedral tilt angles range from 14-61°. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Ba(3), one Ba(4), two equivalent Ba(2), and one Nb(1) atom. In the third O site, O(3) is bonded in a 1-coordinate geometry to one Ba(1), one Ba(5), two equivalent Ba(6), and one Nb(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Ba(6), two equivalent Ba(5), one Nb(2), and one Ir(1) atom. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to one Ba(3), one Ba(6), and three equivalent Ba(1) atoms. In the second Cl site, Cl(2) is bonded to one Ba(1), one Ba(2), and three equivalent Ba(3) atoms to form distorted ClBa5 trigonal bipyramids that share corners with three equivalent O(1)Ba4NbIr octahedra and corners with six equivalent Cl(2)Ba5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 44°.