Pb2Ba3(BO3)3Br crystallizes in the orthorhombic C222_1 space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to one O(3), two equivalent O(2), two equivalent O(4), two equivalent O(5), and two equivalent Br(1) atoms. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), and one Br(1) atom. In the third Ba site, Ba(3) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(3) and two equivalent O(4) atoms. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(5) atom. Pb(1) is bonded in a 3-coordinate geometry to one O(1), one O(4), one O(5), and one Br(1) atom. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Ba(2), one Ba(3), one B(2), and one Pb(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), one Ba(3), and one B(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Ba(1), two equivalent Ba(2), two equivalent Ba(3), and one B(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), one Ba(3), one B(1), and one Pb(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(3), one B(2), and one Pb(1) atom. Br(1) is bonded to one Ba(2), two equivalent Ba(1), and two equivalent Pb(1) atoms to form distorted corner-sharing BrBa3Pb2 trigonal bipyramids.
Pb2Ba3(BO3)3Br crystallizes in the orthorhombic C222_1 space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to one O(3), two equivalent O(2), two equivalent O(4), two equivalent O(5), and two equivalent Br(1) atoms. The Ba(1)-O(3) bond length is 2.66 Å. Both Ba(1)-O(2) bond lengths are 2.86 Å. Both Ba(1)-O(4) bond lengths are 2.97 Å. Both Ba(1)-O(5) bond lengths are 2.81 Å. Both Ba(1)-Br(1) bond lengths are 3.47 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), and one Br(1) atom. Both Ba(2)-O(1) bond lengths are 2.70 Å. Both Ba(2)-O(2) bond lengths are 2.81 Å. Both Ba(2)-O(3) bond lengths are 2.93 Å. Both Ba(2)-O(4) bond lengths are 2.92 Å. The Ba(2)-Br(1) bond length is 3.78 Å. In the third Ba site, Ba(3) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms. Both Ba(3)-O(1) bond lengths are 2.82 Å. Both Ba(3)-O(2) bond lengths are 2.74 Å. Both Ba(3)-O(3) bond lengths are 2.97 Å. Both Ba(3)-O(4) bond lengths are 3.09 Å. Both Ba(3)-O(5) bond lengths are 3.13 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(3) and two equivalent O(4) atoms. The B(1)-O(3) bond length is 1.38 Å. Both B(1)-O(4) bond lengths are 1.40 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(5) atom. The B(2)-O(1) bond length is 1.38 Å. The B(2)-O(2) bond length is 1.38 Å. The B(2)-O(5) bond length is 1.38 Å. Pb(1) is bonded in a 3-coordinate geometry to one O(1), one O(4), one O(5), and one Br(1) atom. The Pb(1)-O(1) bond length is 2.32 Å. The Pb(1)-O(4) bond length is 2.43 Å. The Pb(1)-O(5) bond length is 2.30 Å. The Pb(1)-Br(1) bond length is 3.20 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Ba(2), one Ba(3), one B(2), and one Pb(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), one Ba(3), and one B(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Ba(1), two equivalent Ba(2), two equivalent Ba(3), and one B(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), one Ba(3), one B(1), and one Pb(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(3), one B(2), and one Pb(1) atom. Br(1) is bonded to one Ba(2), two equivalent Ba(1), and two equivalent Pb(1) atoms to form distorted corner-sharing BrBa3Pb2 trigonal bipyramids.