Ba5La3I19 crystallizes in the triclinic P-1 space group. There are five inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to one I(10), one I(11), one I(19), one I(3), one I(5), one I(6), and one I(8) atom to form distorted BaI7 pentagonal bipyramids that share  a cornercorner with one La(2)I6 octahedra, corners with three equivalent La(1)I6 octahedra,  a cornercorner with one Ba(4)I6 pentagonal pyramid, and  an edgeedge with one La(3)I6 octahedra. The corner-sharing octahedral tilt angles range from 32-62°. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one I(10), one I(12), one I(16), one I(3), one I(4), one I(5), one I(7), and one I(9) atom. In the third Ba site, Ba(3) is bonded in a 6-coordinate geometry to one I(11), one I(14), one I(15), one I(18), one I(20), and one I(8) atom. In the fourth Ba site, Ba(4) is bonded to one I(12), one I(15), one I(16), one I(17), one I(19), and one I(4) atom to form distorted BaI6 pentagonal pyramids that share  a cornercorner with one La(2)I6 octahedra,  a cornercorner with one Ba(1)I7 pentagonal bipyramid,  an edgeedge with one La(1)I6 octahedra, and  an edgeedge with one La(3)I6 octahedra. The corner-sharing octahedral tilt angles are 45°. In the fifth Ba site, Ba(5) is bonded in a 8-coordinate geometry to one I(10), one I(11), one I(13), one I(14), one I(16), one I(17), and two equivalent I(20) atoms. There are three inequivalent La sites. In the first La site, La(1) is bonded to one I(13), one I(15), one I(17), one I(5), one I(6), and one I(8) atom to form LaI6 octahedra that share corners with three equivalent Ba(1)I7 pentagonal bipyramids and  an edgeedge with one Ba(4)I6 pentagonal pyramid. In the second La site, La(2) is bonded to one I(10), one I(12), one I(14), one I(20), one I(7), and one I(9) atom to form LaI6 octahedra that share  a cornercorner with one Ba(1)I7 pentagonal bipyramid and  a cornercorner with one Ba(4)I6 pentagonal pyramid. In the third La site, La(3) is bonded to one I(1), one I(18), one I(19), one I(2), one I(3), and one I(4) atom to form LaI6 octahedra that share corners with two equivalent La(3)I6 octahedra,  an edgeedge with one Ba(1)I7 pentagonal bipyramid, and  an edgeedge with one Ba(4)I6 pentagonal pyramid. The corner-sharing octahedra are not tilted. There are twenty inequivalent I sites. In the first I site, I(1) is bonded in a linear geometry to two equivalent La(3) atoms. In the second I site, I(2) is bonded in a linear geometry to two equivalent La(3) atoms. In the third I site, I(3) is bonded in a distorted T-shaped geometry to one Ba(1), one Ba(2), and one La(3) atom. In the fourth I site, I(4) is bonded in a 3-coordinate geometry to one Ba(2), one Ba(4), and one La(3) atom. In the fifth I site, I(5) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ba(2), and one La(1) atom. In the sixth I site, I(6) is bonded in a bent 150 degrees geometry to one Ba(1) and one La(1) atom. In the seventh I site, I(7) is bonded in a bent 120 degrees geometry to one Ba(2) and one La(2) atom. In the eighth I site, I(8) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ba(3), and one La(1) atom. In the ninth I site, I(9) is bonded in a bent 150 degrees geometry to one Ba(2) and one La(2) atom. In the tenth I site, I(10) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(2), one Ba(5), and one La(2) atom. In the eleventh I site, I(11) is bonded in a T-shaped geometry to one Ba(1), one Ba(3), and one Ba(5) atom. In the twelfth I site, I(12) is bonded in a 2-coordinate geometry to one Ba(2), one Ba(4), and one La(2) atom. In the thirteenth I site, I(13) is bonded in a water-like geometry to one Ba(5) and one La(1) atom. In the fourteenth I site, I(14) is bonded in a 3-coordinate geometry to one Ba(3), one Ba(5), and one La(2) atom. In the fifteenth I site, I(15) is bonded in a distorted trigonal planar geometry to one Ba(3), one Ba(4), and one La(1) atom. In the sixteenth I site, I(16) is bonded in a trigonal planar geometry to one Ba(2), one Ba(4), and one Ba(5) atom. In the seventeenth I site, I(17) is bonded in a distorted trigonal non-coplanar geometry to one Ba(4), one Ba(5), and one La(1) atom. In the eighteenth I site, I(18) is bonded in a bent 150 degrees geometry to one Ba(3) and one La(3) atom. In the nineteenth I site, I(19) is bonded in a distorted T-shaped geometry to one Ba(1), one Ba(4), and one La(3) atom. In the twentieth I site, I(20) is bonded to one Ba(3), two equivalent Ba(5), and one La(2) atom to form distorted edge-sharing IBa3La trigonal pyramids.
Ba5La3I19 crystallizes in the triclinic P-1 space group. There are five inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to one I(10), one I(11), one I(19), one I(3), one I(5), one I(6), and one I(8) atom to form distorted BaI7 pentagonal bipyramids that share  a cornercorner with one La(2)I6 octahedra, corners with three equivalent La(1)I6 octahedra,  a cornercorner with one Ba(4)I6 pentagonal pyramid, and  an edgeedge with one La(3)I6 octahedra. The corner-sharing octahedral tilt angles range from 32-62°. The Ba(1)-I(10) bond length is 3.72 Å. The Ba(1)-I(11) bond length is 3.42 Å. The Ba(1)-I(19) bond length is 3.52 Å. The Ba(1)-I(3) bond length is 3.67 Å. The Ba(1)-I(5) bond length is 3.76 Å. The Ba(1)-I(6) bond length is 3.66 Å. The Ba(1)-I(8) bond length is 3.64 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one I(10), one I(12), one I(16), one I(3), one I(4), one I(5), one I(7), and one I(9) atom. The Ba(2)-I(10) bond length is 3.98 Å. The Ba(2)-I(12) bond length is 4.16 Å. The Ba(2)-I(16) bond length is 3.55 Å. The Ba(2)-I(3) bond length is 3.75 Å. The Ba(2)-I(4) bond length is 4.17 Å. The Ba(2)-I(5) bond length is 3.63 Å. The Ba(2)-I(7) bond length is 3.52 Å. The Ba(2)-I(9) bond length is 3.59 Å. In the third Ba site, Ba(3) is bonded in a 6-coordinate geometry to one I(11), one I(14), one I(15), one I(18), one I(20), and one I(8) atom. The Ba(3)-I(11) bond length is 3.39 Å. The Ba(3)-I(14) bond length is 3.55 Å. The Ba(3)-I(15) bond length is 3.46 Å. The Ba(3)-I(18) bond length is 3.41 Å. The Ba(3)-I(20) bond length is 3.79 Å. The Ba(3)-I(8) bond length is 3.70 Å. In the fourth Ba site, Ba(4) is bonded to one I(12), one I(15), one I(16), one I(17), one I(19), and one I(4) atom to form distorted BaI6 pentagonal pyramids that share  a cornercorner with one La(2)I6 octahedra,  a cornercorner with one Ba(1)I7 pentagonal bipyramid,  an edgeedge with one La(1)I6 octahedra, and  an edgeedge with one La(3)I6 octahedra. The corner-sharing octahedral tilt angles are 45°. The Ba(4)-I(12) bond length is 3.57 Å. The Ba(4)-I(15) bond length is 3.59 Å. The Ba(4)-I(16) bond length is 3.44 Å. The Ba(4)-I(17) bond length is 3.60 Å. The Ba(4)-I(19) bond length is 3.53 Å. The Ba(4)-I(4) bond length is 3.55 Å. In the fifth Ba site, Ba(5) is bonded in a 8-coordinate geometry to one I(10), one I(11), one I(13), one I(14), one I(16), one I(17), and two equivalent I(20) atoms. The Ba(5)-I(10) bond length is 3.95 Å. The Ba(5)-I(11) bond length is 3.52 Å. The Ba(5)-I(13) bond length is 3.56 Å. The Ba(5)-I(14) bond length is 3.74 Å. The Ba(5)-I(16) bond length is 3.46 Å. The Ba(5)-I(17) bond length is 3.66 Å. There is one shorter (3.64 Å) and one longer (4.05 Å) Ba(5)-I(20) bond length. There are three inequivalent La sites. In the first La site, La(1) is bonded to one I(13), one I(15), one I(17), one I(5), one I(6), and one I(8) atom to form LaI6 octahedra that share corners with three equivalent Ba(1)I7 pentagonal bipyramids and  an edgeedge with one Ba(4)I6 pentagonal pyramid. The La(1)-I(13) bond length is 3.09 Å. The La(1)-I(15) bond length is 3.30 Å. The La(1)-I(17) bond length is 3.25 Å. The La(1)-I(5) bond length is 3.32 Å. The La(1)-I(6) bond length is 3.10 Å. The La(1)-I(8) bond length is 3.31 Å. In the second La site, La(2) is bonded to one I(10), one I(12), one I(14), one I(20), one I(7), and one I(9) atom to form LaI6 octahedra that share  a cornercorner with one Ba(1)I7 pentagonal bipyramid and  a cornercorner with one Ba(4)I6 pentagonal pyramid. The La(2)-I(10) bond length is 3.29 Å. The La(2)-I(12) bond length is 3.24 Å. The La(2)-I(14) bond length is 3.26 Å. The La(2)-I(20) bond length is 3.21 Å. The La(2)-I(7) bond length is 3.13 Å. The La(2)-I(9) bond length is 3.09 Å. In the third La site, La(3) is bonded to one I(1), one I(18), one I(19), one I(2), one I(3), and one I(4) atom to form LaI6 octahedra that share corners with two equivalent La(3)I6 octahedra,  an edgeedge with one Ba(1)I7 pentagonal bipyramid, and  an edgeedge with one Ba(4)I6 pentagonal pyramid. The corner-sharing octahedra are not tilted. The La(3)-I(1) bond length is 3.02 Å. The La(3)-I(18) bond length is 3.10 Å. The La(3)-I(19) bond length is 3.24 Å. The La(3)-I(2) bond length is 3.01 Å. The La(3)-I(3) bond length is 3.21 Å. The La(3)-I(4) bond length is 3.20 Å. There are twenty inequivalent I sites. In the first I site, I(1) is bonded in a linear geometry to two equivalent La(3) atoms. In the second I site, I(2) is bonded in a linear geometry to two equivalent La(3) atoms. In the third I site, I(3) is bonded in a distorted T-shaped geometry to one Ba(1), one Ba(2), and one La(3) atom. In the fourth I site, I(4) is bonded in a 3-coordinate geometry to one Ba(2), one Ba(4), and one La(3) atom. In the fifth I site, I(5) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ba(2), and one La(1) atom. In the sixth I site, I(6) is bonded in a bent 150 degrees geometry to one Ba(1) and one La(1) atom. In the seventh I site, I(7) is bonded in a bent 120 degrees geometry to one Ba(2) and one La(2) atom. In the eighth I site, I(8) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ba(3), and one La(1) atom. In the ninth I site, I(9) is bonded in a bent 150 degrees geometry to one Ba(2) and one La(2) atom. In the tenth I site, I(10) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(2), one Ba(5), and one La(2) atom. In the eleventh I site, I(11) is bonded in a T-shaped geometry to one Ba(1), one Ba(3), and one Ba(5) atom. In the twelfth I site, I(12) is bonded in a 2-coordinate geometry to one Ba(2), one Ba(4), and one La(2) atom. In the thirteenth I site, I(13) is bonded in a water-like geometry to one Ba(5) and one La(1) atom. In the fourteenth I site, I(14) is bonded in a 3-coordinate geometry to one Ba(3), one Ba(5), and one La(2) atom. In the fifteenth I site, I(15) is bonded in a distorted trigonal planar geometry to one Ba(3), one Ba(4), and one La(1) atom. In the sixteenth I site, I(16) is bonded in a trigonal planar geometry to one Ba(2), one Ba(4), and one Ba(5) atom. In the seventeenth I site, I(17) is bonded in a distorted trigonal non-coplanar geometry to one Ba(4), one Ba(5), and one La(1) atom. In the eighteenth I site, I(18) is bonded in a bent 150 degrees geometry to one Ba(3) and one La(3) atom. In the nineteenth I site, I(19) is bonded in a distorted T-shaped geometry to one Ba(1), one Ba(4), and one La(3) atom. In the twentieth I site, I(20) is bonded to one Ba(3), two equivalent Ba(5), and one La(2) atom to form distorted edge-sharing IBa3La trigonal pyramids.