Ba5Re3O15Br crystallizes in the hexagonal P6_3cm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 11-coordinate geometry to two equivalent O(1), three equivalent O(3), four equivalent O(2), and two equivalent Br(1) atoms. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to three equivalent O(2) and six equivalent O(1) atoms. Re(1) is bonded in a distorted trigonal bipyramidal geometry to one O(3), two equivalent O(1), and two equivalent O(2) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Ba(1), two equivalent Ba(2), and one Re(1) atom to form distorted OBa3Re tetrahedra that share corners with two equivalent Br(1)Ba6 octahedra, corners with six equivalent O(1)Ba3Re tetrahedra, corners with six equivalent O(2)Ba3Re tetrahedra, edges with three equivalent O(1)Ba3Re tetrahedra, and edges with three equivalent O(2)Ba3Re tetrahedra. The corner-sharing octahedral tilt angles range from 42-43°. In the second O site, O(2) is bonded to one Ba(2), two equivalent Ba(1), and one Re(1) atom to form distorted OBa3Re tetrahedra that share corners with two equivalent Br(1)Ba6 octahedra, corners with six equivalent O(1)Ba3Re tetrahedra, corners with seven equivalent O(2)Ba3Re tetrahedra,  an edgeedge with one Br(1)Ba6 octahedra,  an edgeedge with one O(2)Ba3Re tetrahedra, and edges with three equivalent O(1)Ba3Re tetrahedra. The corner-sharing octahedral tilt angles range from 50-73°. In the third O site, O(3) is bonded in a single-bond geometry to three equivalent Ba(1) and one Re(1) atom. Br(1) is bonded to six equivalent Ba(1) atoms to form BrBa6 octahedra that share corners with twelve equivalent O(1)Ba3Re tetrahedra, corners with twelve equivalent O(2)Ba3Re tetrahedra, edges with six equivalent O(2)Ba3Re tetrahedra, and faces with two equivalent Br(1)Ba6 octahedra.
Ba5Re3O15Br crystallizes in the hexagonal P6_3cm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 11-coordinate geometry to two equivalent O(1), three equivalent O(3), four equivalent O(2), and two equivalent Br(1) atoms. Both Ba(1)-O(1) bond lengths are 2.76 Å. There is one shorter (3.02 Å) and two longer (3.33 Å) Ba(1)-O(3) bond lengths. There are two shorter (2.80 Å) and two longer (2.95 Å) Ba(1)-O(2) bond lengths. There is one shorter (3.50 Å) and one longer (3.70 Å) Ba(1)-Br(1) bond length. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to three equivalent O(2) and six equivalent O(1) atoms. All Ba(2)-O(2) bond lengths are 2.82 Å. There are three shorter (2.76 Å) and three longer (2.84 Å) Ba(2)-O(1) bond lengths. Re(1) is bonded in a distorted trigonal bipyramidal geometry to one O(3), two equivalent O(1), and two equivalent O(2) atoms. The Re(1)-O(3) bond length is 1.76 Å. Both Re(1)-O(1) bond lengths are 1.87 Å. Both Re(1)-O(2) bond lengths are 1.85 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Ba(1), two equivalent Ba(2), and one Re(1) atom to form distorted OBa3Re tetrahedra that share corners with two equivalent Br(1)Ba6 octahedra, corners with six equivalent O(1)Ba3Re tetrahedra, corners with six equivalent O(2)Ba3Re tetrahedra, edges with three equivalent O(1)Ba3Re tetrahedra, and edges with three equivalent O(2)Ba3Re tetrahedra. The corner-sharing octahedral tilt angles range from 42-43°. In the second O site, O(2) is bonded to one Ba(2), two equivalent Ba(1), and one Re(1) atom to form distorted OBa3Re tetrahedra that share corners with two equivalent Br(1)Ba6 octahedra, corners with six equivalent O(1)Ba3Re tetrahedra, corners with seven equivalent O(2)Ba3Re tetrahedra,  an edgeedge with one Br(1)Ba6 octahedra,  an edgeedge with one O(2)Ba3Re tetrahedra, and edges with three equivalent O(1)Ba3Re tetrahedra. The corner-sharing octahedral tilt angles range from 50-73°. In the third O site, O(3) is bonded in a single-bond geometry to three equivalent Ba(1) and one Re(1) atom. Br(1) is bonded to six equivalent Ba(1) atoms to form BrBa6 octahedra that share corners with twelve equivalent O(1)Ba3Re tetrahedra, corners with twelve equivalent O(2)Ba3Re tetrahedra, edges with six equivalent O(2)Ba3Re tetrahedra, and faces with two equivalent Br(1)Ba6 octahedra.