Ba6Ca11I34 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 5-coordinate geometry to one I(15), one I(17), one I(2), one I(4), and two equivalent I(8) atoms. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to one I(13), one I(14), one I(17), one I(3), one I(5), one I(8), and one I(9) atom. In the third Ba site, Ba(3) is bonded in a 6-coordinate geometry to one I(1), one I(11), one I(13), one I(15), one I(16), and one I(4) atom. There are six inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent I(10), two equivalent I(13), and two equivalent I(3) atoms to form a mixture of corner and edge-sharing CaI6 octahedra. The corner-sharing octahedral tilt angles range from 52-56°. In the second Ca site, Ca(2) is bonded to one I(1), one I(10), one I(13), one I(15), one I(4), and one I(5) atom to form a mixture of corner and edge-sharing CaI6 octahedra. The corner-sharing octahedral tilt angles range from 47-63°. In the third Ca site, Ca(3) is bonded to one I(1), one I(12), one I(16), one I(5), one I(6), and one I(8) atom to form a mixture of corner and edge-sharing CaI6 octahedra. The corner-sharing octahedral tilt angles range from 11-63°. In the fourth Ca site, Ca(4) is bonded to one I(11), one I(2), one I(3), one I(4), one I(7), and one I(9) atom to form a mixture of corner and edge-sharing CaI6 octahedra. The corner-sharing octahedral tilt angles range from 23-55°. In the fifth Ca site, Ca(5) is bonded to one I(12), one I(14), one I(17), one I(2), one I(6), and one I(7) atom to form a mixture of corner and edge-sharing CaI6 octahedra. The corner-sharing octahedral tilt angles range from 11-44°. In the sixth Ca site, Ca(6) is bonded to one I(10), one I(11), one I(12), one I(14), one I(16), and one I(9) atom to form a mixture of corner and edge-sharing CaI6 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. There are seventeen inequivalent I sites. In the first I site, I(1) is bonded in a trigonal planar geometry to one Ba(3), one Ca(2), and one Ca(3) atom. In the second I site, I(2) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ca(4), and one Ca(5) atom. In the third I site, I(3) is bonded in a distorted bent 120 degrees geometry to one Ba(2), one Ca(1), and one Ca(4) atom. In the fourth I site, I(4) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(3), one Ca(2), and one Ca(4) atom. In the fifth I site, I(5) is bonded in a distorted trigonal non-coplanar geometry to one Ba(2), one Ca(2), and one Ca(3) atom. In the sixth I site, I(6) is bonded in a distorted bent 150 degrees geometry to one Ca(3) and one Ca(5) atom. In the seventh I site, I(7) is bonded in a bent 150 degrees geometry to one Ca(4) and one Ca(5) atom. In the eighth I site, I(8) is bonded in a 4-coordinate geometry to one Ba(2), two equivalent Ba(1), and one Ca(3) atom. In the ninth I site, I(9) is bonded in a distorted L-shaped geometry to one Ba(2), one Ca(4), and one Ca(6) atom. In the tenth I site, I(10) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one Ca(6) atom. In the eleventh I site, I(11) is bonded in a 3-coordinate geometry to one Ba(3), one Ca(4), and one Ca(6) atom. In the twelfth I site, I(12) is bonded in a T-shaped geometry to one Ca(3), one Ca(5), and one Ca(6) atom. In the thirteenth I site, I(13) is bonded to one Ba(2), one Ba(3), one Ca(1), and one Ca(2) atom to form corner-sharing IBa2Ca2 trigonal pyramids. In the fourteenth I site, I(14) is bonded in a distorted trigonal planar geometry to one Ba(2), one Ca(5), and one Ca(6) atom. In the fifteenth I site, I(15) is bonded in a distorted T-shaped geometry to one Ba(1), one Ba(3), and one Ca(2) atom. In the sixteenth I site, I(16) is bonded in a distorted T-shaped geometry to one Ba(3), one Ca(3), and one Ca(6) atom. In the seventeenth I site, I(17) is bonded in a distorted trigonal non-coplanar geometry to one Ba(1), one Ba(2), and one Ca(5) atom.
Ba6Ca11I34 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 5-coordinate geometry to one I(15), one I(17), one I(2), one I(4), and two equivalent I(8) atoms. The Ba(1)-I(15) bond length is 3.54 Å. The Ba(1)-I(17) bond length is 3.81 Å. The Ba(1)-I(2) bond length is 3.71 Å. The Ba(1)-I(4) bond length is 3.78 Å. There is one shorter (3.68 Å) and one longer (4.19 Å) Ba(1)-I(8) bond length. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to one I(13), one I(14), one I(17), one I(3), one I(5), one I(8), and one I(9) atom. The Ba(2)-I(13) bond length is 3.72 Å. The Ba(2)-I(14) bond length is 3.64 Å. The Ba(2)-I(17) bond length is 3.52 Å. The Ba(2)-I(3) bond length is 4.12 Å. The Ba(2)-I(5) bond length is 3.67 Å. The Ba(2)-I(8) bond length is 3.69 Å. The Ba(2)-I(9) bond length is 4.09 Å. In the third Ba site, Ba(3) is bonded in a 6-coordinate geometry to one I(1), one I(11), one I(13), one I(15), one I(16), and one I(4) atom. The Ba(3)-I(1) bond length is 3.67 Å. The Ba(3)-I(11) bond length is 3.92 Å. The Ba(3)-I(13) bond length is 3.86 Å. The Ba(3)-I(15) bond length is 3.51 Å. The Ba(3)-I(16) bond length is 3.58 Å. The Ba(3)-I(4) bond length is 3.50 Å. There are six inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent I(10), two equivalent I(13), and two equivalent I(3) atoms to form a mixture of corner and edge-sharing CaI6 octahedra. The corner-sharing octahedral tilt angles range from 52-56°. Both Ca(1)-I(10) bond lengths are 3.13 Å. Both Ca(1)-I(13) bond lengths are 3.24 Å. Both Ca(1)-I(3) bond lengths are 3.06 Å. In the second Ca site, Ca(2) is bonded to one I(1), one I(10), one I(13), one I(15), one I(4), and one I(5) atom to form a mixture of corner and edge-sharing CaI6 octahedra. The corner-sharing octahedral tilt angles range from 47-63°. The Ca(2)-I(1) bond length is 3.13 Å. The Ca(2)-I(10) bond length is 3.08 Å. The Ca(2)-I(13) bond length is 3.20 Å. The Ca(2)-I(15) bond length is 3.08 Å. The Ca(2)-I(4) bond length is 3.23 Å. The Ca(2)-I(5) bond length is 3.13 Å. In the third Ca site, Ca(3) is bonded to one I(1), one I(12), one I(16), one I(5), one I(6), and one I(8) atom to form a mixture of corner and edge-sharing CaI6 octahedra. The corner-sharing octahedral tilt angles range from 11-63°. The Ca(3)-I(1) bond length is 3.20 Å. The Ca(3)-I(12) bond length is 3.06 Å. The Ca(3)-I(16) bond length is 3.15 Å. The Ca(3)-I(5) bond length is 3.07 Å. The Ca(3)-I(6) bond length is 3.14 Å. The Ca(3)-I(8) bond length is 3.19 Å. In the fourth Ca site, Ca(4) is bonded to one I(11), one I(2), one I(3), one I(4), one I(7), and one I(9) atom to form a mixture of corner and edge-sharing CaI6 octahedra. The corner-sharing octahedral tilt angles range from 23-55°. The Ca(4)-I(11) bond length is 3.19 Å. The Ca(4)-I(2) bond length is 3.19 Å. The Ca(4)-I(3) bond length is 3.11 Å. The Ca(4)-I(4) bond length is 3.19 Å. The Ca(4)-I(7) bond length is 3.09 Å. The Ca(4)-I(9) bond length is 3.14 Å. In the fifth Ca site, Ca(5) is bonded to one I(12), one I(14), one I(17), one I(2), one I(6), and one I(7) atom to form a mixture of corner and edge-sharing CaI6 octahedra. The corner-sharing octahedral tilt angles range from 11-44°. The Ca(5)-I(12) bond length is 3.09 Å. The Ca(5)-I(14) bond length is 3.18 Å. The Ca(5)-I(17) bond length is 3.22 Å. The Ca(5)-I(2) bond length is 3.21 Å. The Ca(5)-I(6) bond length is 3.16 Å. The Ca(5)-I(7) bond length is 3.02 Å. In the sixth Ca site, Ca(6) is bonded to one I(10), one I(11), one I(12), one I(14), one I(16), and one I(9) atom to form a mixture of corner and edge-sharing CaI6 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. The Ca(6)-I(10) bond length is 3.15 Å. The Ca(6)-I(11) bond length is 3.10 Å. The Ca(6)-I(12) bond length is 3.13 Å. The Ca(6)-I(14) bond length is 3.19 Å. The Ca(6)-I(16) bond length is 3.18 Å. The Ca(6)-I(9) bond length is 3.13 Å. There are seventeen inequivalent I sites. In the first I site, I(1) is bonded in a trigonal planar geometry to one Ba(3), one Ca(2), and one Ca(3) atom. In the second I site, I(2) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ca(4), and one Ca(5) atom. In the third I site, I(3) is bonded in a distorted bent 120 degrees geometry to one Ba(2), one Ca(1), and one Ca(4) atom. In the fourth I site, I(4) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(3), one Ca(2), and one Ca(4) atom. In the fifth I site, I(5) is bonded in a distorted trigonal non-coplanar geometry to one Ba(2), one Ca(2), and one Ca(3) atom. In the sixth I site, I(6) is bonded in a distorted bent 150 degrees geometry to one Ca(3) and one Ca(5) atom. In the seventh I site, I(7) is bonded in a bent 150 degrees geometry to one Ca(4) and one Ca(5) atom. In the eighth I site, I(8) is bonded in a 4-coordinate geometry to one Ba(2), two equivalent Ba(1), and one Ca(3) atom. In the ninth I site, I(9) is bonded in a distorted L-shaped geometry to one Ba(2), one Ca(4), and one Ca(6) atom. In the tenth I site, I(10) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one Ca(6) atom. In the eleventh I site, I(11) is bonded in a 3-coordinate geometry to one Ba(3), one Ca(4), and one Ca(6) atom. In the twelfth I site, I(12) is bonded in a T-shaped geometry to one Ca(3), one Ca(5), and one Ca(6) atom. In the thirteenth I site, I(13) is bonded to one Ba(2), one Ba(3), one Ca(1), and one Ca(2) atom to form corner-sharing IBa2Ca2 trigonal pyramids. In the fourteenth I site, I(14) is bonded in a distorted trigonal planar geometry to one Ba(2), one Ca(5), and one Ca(6) atom. In the fifteenth I site, I(15) is bonded in a distorted T-shaped geometry to one Ba(1), one Ba(3), and one Ca(2) atom. In the sixteenth I site, I(16) is bonded in a distorted T-shaped geometry to one Ba(3), one Ca(3), and one Ca(6) atom. In the seventeenth I site, I(17) is bonded in a distorted trigonal non-coplanar geometry to one Ba(1), one Ba(2), and one Ca(5) atom.