Ba5Ru2Br2O9 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 7-coordinate geometry to three equivalent O(1) and four equivalent Br(1) atoms. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to three equivalent O(2), six equivalent O(1), and one Br(1) atom. In the third Ba site, Ba(3) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form BaO12 cuboctahedra that share corners with six equivalent Ba(3)O12 cuboctahedra and faces with six equivalent Ru(1)O6 octahedra. Ru(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form RuO6 octahedra that share faces with three equivalent Ba(3)O12 cuboctahedra and  a faceface with one Ru(1)O6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(3), two equivalent Ba(2), and one Ru(1) atom. In the second O site, O(2) is bonded to two equivalent Ba(2), two equivalent Ba(3), and two equivalent Ru(1) atoms to form a mixture of distorted face and corner-sharing OBa4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 6-60°. Br(1) is bonded in a distorted pentagonal planar geometry to one Ba(2) and four equivalent Ba(1) atoms.
Ba5Ru2Br2O9 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 7-coordinate geometry to three equivalent O(1) and four equivalent Br(1) atoms. All Ba(1)-O(1) bond lengths are 2.58 Å. There is one shorter (3.43 Å) and three longer (3.58 Å) Ba(1)-Br(1) bond lengths. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to three equivalent O(2), six equivalent O(1), and one Br(1) atom. All Ba(2)-O(2) bond lengths are 2.73 Å. All Ba(2)-O(1) bond lengths are 3.00 Å. The Ba(2)-Br(1) bond length is 3.31 Å. In the third Ba site, Ba(3) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form BaO12 cuboctahedra that share corners with six equivalent Ba(3)O12 cuboctahedra and faces with six equivalent Ru(1)O6 octahedra. All Ba(3)-O(1) bond lengths are 2.98 Å. All Ba(3)-O(2) bond lengths are 2.97 Å. Ru(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form RuO6 octahedra that share faces with three equivalent Ba(3)O12 cuboctahedra and  a faceface with one Ru(1)O6 octahedra. All Ru(1)-O(1) bond lengths are 1.90 Å. All Ru(1)-O(2) bond lengths are 2.11 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(3), two equivalent Ba(2), and one Ru(1) atom. In the second O site, O(2) is bonded to two equivalent Ba(2), two equivalent Ba(3), and two equivalent Ru(1) atoms to form a mixture of distorted face and corner-sharing OBa4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 6-60°. Br(1) is bonded in a distorted pentagonal planar geometry to one Ba(2) and four equivalent Ba(1) atoms.