Ba3LaBr9 crystallizes in the monoclinic Pc space group. There are six inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to one Br(1), one Br(10), one Br(13), one Br(14), one Br(4), one Br(5), and one Br(9) atom to form distorted BaBr7 pentagonal bipyramids that share corners with two equivalent La(2)Br7 pentagonal bipyramids. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one Br(11), one Br(12), one Br(15), one Br(2), one Br(3), one Br(6), one Br(7), and one Br(8) atom. In the third Ba site, Ba(3) is bonded in a 7-coordinate geometry to one Br(12), one Br(13), one Br(17), one Br(18), one Br(3), one Br(8), and one Br(9) atom. In the fourth Ba site, Ba(4) is bonded in a 8-coordinate geometry to one Br(1), one Br(10), one Br(11), one Br(14), one Br(15), one Br(16), one Br(2), and one Br(7) atom. In the fifth Ba site, Ba(5) is bonded in a 8-coordinate geometry to one Br(11), one Br(12), one Br(15), one Br(16), one Br(17), one Br(2), one Br(3), and one Br(6) atom. In the sixth Ba site, Ba(6) is bonded in a 7-coordinate geometry to one Br(1), one Br(10), one Br(13), one Br(14), one Br(18), one Br(4), and one Br(5) atom. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 8-coordinate geometry to one Br(1), one Br(10), one Br(11), one Br(16), one Br(2), one Br(5), one Br(6), and one Br(7) atom. In the second La site, La(2) is bonded to one Br(12), one Br(17), one Br(18), one Br(3), one Br(4), one Br(8), and one Br(9) atom to form distorted LaBr7 pentagonal bipyramids that share corners with two equivalent Ba(1)Br7 pentagonal bipyramids. There are eighteen inequivalent Br sites. In the first Br site, Br(1) is bonded to one Ba(1), one Ba(4), one Ba(6), and one La(1) atom to form a mixture of edge and corner-sharing BrBa3La tetrahedra. In the second Br site, Br(2) is bonded to one Ba(2), one Ba(4), one Ba(5), and one La(1) atom to form a mixture of edge and corner-sharing BrBa3La tetrahedra. In the third Br site, Br(3) is bonded to one Ba(2), one Ba(3), one Ba(5), and one La(2) atom to form a mixture of edge and corner-sharing BrBa3La tetrahedra. In the fourth Br site, Br(4) is bonded in a distorted trigonal non-coplanar geometry to one Ba(1), one Ba(6), and one La(2) atom. In the fifth Br site, Br(5) is bonded in a trigonal planar geometry to one Ba(1), one Ba(6), and one La(1) atom. In the sixth Br site, Br(6) is bonded in a trigonal non-coplanar geometry to one Ba(2), one Ba(5), and one La(1) atom. In the seventh Br site, Br(7) is bonded in a distorted trigonal non-coplanar geometry to one Ba(2), one Ba(4), and one La(1) atom. In the eighth Br site, Br(8) is bonded in a distorted trigonal planar geometry to one Ba(2), one Ba(3), and one La(2) atom. In the ninth Br site, Br(9) is bonded in a trigonal non-coplanar geometry to one Ba(1), one Ba(3), and one La(2) atom. In the tenth Br site, Br(10) is bonded to one Ba(1), one Ba(4), one Ba(6), and one La(1) atom to form a mixture of distorted edge and corner-sharing BrBa3La tetrahedra. In the eleventh Br site, Br(11) is bonded to one Ba(2), one Ba(4), one Ba(5), and one La(1) atom to form a mixture of distorted edge and corner-sharing BrBa3La tetrahedra. In the twelfth Br site, Br(12) is bonded to one Ba(2), one Ba(3), one Ba(5), and one La(2) atom to form a mixture of edge and corner-sharing BrBa3La tetrahedra. In the thirteenth Br site, Br(13) is bonded in a trigonal non-coplanar geometry to one Ba(1), one Ba(3), and one Ba(6) atom. In the fourteenth Br site, Br(14) is bonded in a trigonal planar geometry to one Ba(1), one Ba(4), and one Ba(6) atom. In the fifteenth Br site, Br(15) is bonded in a distorted trigonal non-coplanar geometry to one Ba(2), one Ba(4), and one Ba(5) atom. In the sixteenth Br site, Br(16) is bonded in a distorted trigonal non-coplanar geometry to one Ba(4), one Ba(5), and one La(1) atom. In the seventeenth Br site, Br(17) is bonded in a trigonal planar geometry to one Ba(3), one Ba(5), and one La(2) atom. In the eighteenth Br site, Br(18) is bonded in a trigonal non-coplanar geometry to one Ba(3), one Ba(6), and one La(2) atom.
Ba3LaBr9 crystallizes in the monoclinic Pc space group. There are six inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to one Br(1), one Br(10), one Br(13), one Br(14), one Br(4), one Br(5), and one Br(9) atom to form distorted BaBr7 pentagonal bipyramids that share corners with two equivalent La(2)Br7 pentagonal bipyramids. The Ba(1)-Br(1) bond length is 3.38 Å. The Ba(1)-Br(10) bond length is 3.38 Å. The Ba(1)-Br(13) bond length is 3.26 Å. The Ba(1)-Br(14) bond length is 3.24 Å. The Ba(1)-Br(4) bond length is 3.31 Å. The Ba(1)-Br(5) bond length is 3.30 Å. The Ba(1)-Br(9) bond length is 3.34 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one Br(11), one Br(12), one Br(15), one Br(2), one Br(3), one Br(6), one Br(7), and one Br(8) atom. The Ba(2)-Br(11) bond length is 3.38 Å. The Ba(2)-Br(12) bond length is 3.44 Å. The Ba(2)-Br(15) bond length is 3.23 Å. The Ba(2)-Br(2) bond length is 3.31 Å. The Ba(2)-Br(3) bond length is 3.35 Å. The Ba(2)-Br(6) bond length is 3.23 Å. The Ba(2)-Br(7) bond length is 3.51 Å. The Ba(2)-Br(8) bond length is 3.37 Å. In the third Ba site, Ba(3) is bonded in a 7-coordinate geometry to one Br(12), one Br(13), one Br(17), one Br(18), one Br(3), one Br(8), and one Br(9) atom. The Ba(3)-Br(12) bond length is 3.36 Å. The Ba(3)-Br(13) bond length is 3.20 Å. The Ba(3)-Br(17) bond length is 3.30 Å. The Ba(3)-Br(18) bond length is 3.32 Å. The Ba(3)-Br(3) bond length is 3.40 Å. The Ba(3)-Br(8) bond length is 3.36 Å. The Ba(3)-Br(9) bond length is 3.38 Å. In the fourth Ba site, Ba(4) is bonded in a 8-coordinate geometry to one Br(1), one Br(10), one Br(11), one Br(14), one Br(15), one Br(16), one Br(2), and one Br(7) atom. The Ba(4)-Br(1) bond length is 3.37 Å. The Ba(4)-Br(10) bond length is 3.51 Å. The Ba(4)-Br(11) bond length is 3.37 Å. The Ba(4)-Br(14) bond length is 3.22 Å. The Ba(4)-Br(15) bond length is 3.59 Å. The Ba(4)-Br(16) bond length is 3.31 Å. The Ba(4)-Br(2) bond length is 3.31 Å. The Ba(4)-Br(7) bond length is 3.26 Å. In the fifth Ba site, Ba(5) is bonded in a 8-coordinate geometry to one Br(11), one Br(12), one Br(15), one Br(16), one Br(17), one Br(2), one Br(3), and one Br(6) atom. The Ba(5)-Br(11) bond length is 3.37 Å. The Ba(5)-Br(12) bond length is 3.43 Å. The Ba(5)-Br(15) bond length is 3.26 Å. The Ba(5)-Br(16) bond length is 3.50 Å. The Ba(5)-Br(17) bond length is 3.33 Å. The Ba(5)-Br(2) bond length is 3.43 Å. The Ba(5)-Br(3) bond length is 3.51 Å. The Ba(5)-Br(6) bond length is 3.21 Å. In the sixth Ba site, Ba(6) is bonded in a 7-coordinate geometry to one Br(1), one Br(10), one Br(13), one Br(14), one Br(18), one Br(4), and one Br(5) atom. The Ba(6)-Br(1) bond length is 3.36 Å. The Ba(6)-Br(10) bond length is 3.51 Å. The Ba(6)-Br(13) bond length is 3.21 Å. The Ba(6)-Br(14) bond length is 3.19 Å. The Ba(6)-Br(18) bond length is 3.35 Å. The Ba(6)-Br(4) bond length is 3.34 Å. The Ba(6)-Br(5) bond length is 3.31 Å. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 8-coordinate geometry to one Br(1), one Br(10), one Br(11), one Br(16), one Br(2), one Br(5), one Br(6), and one Br(7) atom. The La(1)-Br(1) bond length is 3.23 Å. The La(1)-Br(10) bond length is 3.17 Å. The La(1)-Br(11) bond length is 3.17 Å. The La(1)-Br(16) bond length is 2.99 Å. The La(1)-Br(2) bond length is 3.15 Å. The La(1)-Br(5) bond length is 3.06 Å. The La(1)-Br(6) bond length is 3.24 Å. The La(1)-Br(7) bond length is 2.97 Å. In the second La site, La(2) is bonded to one Br(12), one Br(17), one Br(18), one Br(3), one Br(4), one Br(8), and one Br(9) atom to form distorted LaBr7 pentagonal bipyramids that share corners with two equivalent Ba(1)Br7 pentagonal bipyramids. The La(2)-Br(12) bond length is 3.20 Å. The La(2)-Br(17) bond length is 3.02 Å. The La(2)-Br(18) bond length is 3.05 Å. The La(2)-Br(3) bond length is 3.12 Å. The La(2)-Br(4) bond length is 3.00 Å. The La(2)-Br(8) bond length is 3.02 Å. The La(2)-Br(9) bond length is 3.01 Å. There are eighteen inequivalent Br sites. In the first Br site, Br(1) is bonded to one Ba(1), one Ba(4), one Ba(6), and one La(1) atom to form a mixture of edge and corner-sharing BrBa3La tetrahedra. In the second Br site, Br(2) is bonded to one Ba(2), one Ba(4), one Ba(5), and one La(1) atom to form a mixture of edge and corner-sharing BrBa3La tetrahedra. In the third Br site, Br(3) is bonded to one Ba(2), one Ba(3), one Ba(5), and one La(2) atom to form a mixture of edge and corner-sharing BrBa3La tetrahedra. In the fourth Br site, Br(4) is bonded in a distorted trigonal non-coplanar geometry to one Ba(1), one Ba(6), and one La(2) atom. In the fifth Br site, Br(5) is bonded in a trigonal planar geometry to one Ba(1), one Ba(6), and one La(1) atom. In the sixth Br site, Br(6) is bonded in a trigonal non-coplanar geometry to one Ba(2), one Ba(5), and one La(1) atom. In the seventh Br site, Br(7) is bonded in a distorted trigonal non-coplanar geometry to one Ba(2), one Ba(4), and one La(1) atom. In the eighth Br site, Br(8) is bonded in a distorted trigonal planar geometry to one Ba(2), one Ba(3), and one La(2) atom. In the ninth Br site, Br(9) is bonded in a trigonal non-coplanar geometry to one Ba(1), one Ba(3), and one La(2) atom. In the tenth Br site, Br(10) is bonded to one Ba(1), one Ba(4), one Ba(6), and one La(1) atom to form a mixture of distorted edge and corner-sharing BrBa3La tetrahedra. In the eleventh Br site, Br(11) is bonded to one Ba(2), one Ba(4), one Ba(5), and one La(1) atom to form a mixture of distorted edge and corner-sharing BrBa3La tetrahedra. In the twelfth Br site, Br(12) is bonded to one Ba(2), one Ba(3), one Ba(5), and one La(2) atom to form a mixture of edge and corner-sharing BrBa3La tetrahedra. In the thirteenth Br site, Br(13) is bonded in a trigonal non-coplanar geometry to one Ba(1), one Ba(3), and one Ba(6) atom. In the fourteenth Br site, Br(14) is bonded in a trigonal planar geometry to one Ba(1), one Ba(4), and one Ba(6) atom. In the fifteenth Br site, Br(15) is bonded in a distorted trigonal non-coplanar geometry to one Ba(2), one Ba(4), and one Ba(5) atom. In the sixteenth Br site, Br(16) is bonded in a distorted trigonal non-coplanar geometry to one Ba(4), one Ba(5), and one La(1) atom. In the seventeenth Br site, Br(17) is bonded in a trigonal planar geometry to one Ba(3), one Ba(5), and one La(2) atom. In the eighteenth Br site, Br(18) is bonded in a trigonal non-coplanar geometry to one Ba(3), one Ba(6), and one La(2) atom.