Ba5P3O12Br crystallizes in the hexagonal P6_3/m space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to three equivalent O(1), three equivalent O(2), and three equivalent O(3) atoms. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one O(2), one O(3), four equivalent O(1), and two equivalent Br(1) atoms. P(1) is bonded in a tetrahedral geometry to one O(2), one O(3), and two equivalent O(1) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Ba(1), two equivalent Ba(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Ba(2), two equivalent Ba(1), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ba(2), two equivalent Ba(1), and one P(1) atom. Br(1) is bonded to six equivalent Ba(2) atoms to form face-sharing BrBa6 octahedra.
Ba5P3O12Br crystallizes in the hexagonal P6_3/m space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to three equivalent O(1), three equivalent O(2), and three equivalent O(3) atoms. All Ba(1)-O(1) bond lengths are 3.05 Å. All Ba(1)-O(2) bond lengths are 2.82 Å. All Ba(1)-O(3) bond lengths are 2.76 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one O(2), one O(3), four equivalent O(1), and two equivalent Br(1) atoms. The Ba(2)-O(2) bond length is 3.08 Å. The Ba(2)-O(3) bond length is 2.61 Å. There are two shorter (2.76 Å) and two longer (2.91 Å) Ba(2)-O(1) bond lengths. Both Ba(2)-Br(1) bond lengths are 3.36 Å. P(1) is bonded in a tetrahedral geometry to one O(2), one O(3), and two equivalent O(1) atoms. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.57 Å. Both P(1)-O(1) bond lengths are 1.56 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Ba(1), two equivalent Ba(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Ba(2), two equivalent Ba(1), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ba(2), two equivalent Ba(1), and one P(1) atom. Br(1) is bonded to six equivalent Ba(2) atoms to form face-sharing BrBa6 octahedra.