Ba3(OBr)2 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 4-coordinate geometry to four equivalent O(1), one Br(1), and two equivalent Br(2) atoms. In the second Ba site, Ba(2) is bonded in a 2-coordinate geometry to two equivalent O(1), one Br(1), and three equivalent Br(2) atoms. In the third Ba site, Ba(3) is bonded in a 2-coordinate geometry to two equivalent O(1), two equivalent Br(2), and three equivalent Br(1) atoms. O(1) is bonded to one Ba(2), one Ba(3), and two equivalent Ba(1) atoms to form OBa4 tetrahedra that share corners with two equivalent O(1)Ba4 tetrahedra, corners with four equivalent Br(1)Ba5 trigonal bipyramids, edges with three equivalent O(1)Ba4 tetrahedra, and  an edgeedge with one Br(1)Ba5 trigonal bipyramid. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to one Ba(1), one Ba(2), and three equivalent Ba(3) atoms to form distorted BrBa5 trigonal bipyramids that share corners with eight equivalent O(1)Ba4 tetrahedra, corners with two equivalent Br(1)Ba5 trigonal bipyramids, edges with two equivalent O(1)Ba4 tetrahedra, and edges with two equivalent Br(1)Ba5 trigonal bipyramids. In the second Br site, Br(2) is bonded in a 7-coordinate geometry to two equivalent Ba(1), two equivalent Ba(3), and three equivalent Ba(2) atoms.
Ba3(OBr)2 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 4-coordinate geometry to four equivalent O(1), one Br(1), and two equivalent Br(2) atoms. There are two shorter (2.61 Å) and two longer (2.62 Å) Ba(1)-O(1) bond lengths. The Ba(1)-Br(1) bond length is 3.57 Å. Both Ba(1)-Br(2) bond lengths are 3.97 Å. In the second Ba site, Ba(2) is bonded in a 2-coordinate geometry to two equivalent O(1), one Br(1), and three equivalent Br(2) atoms. Both Ba(2)-O(1) bond lengths are 2.42 Å. The Ba(2)-Br(1) bond length is 3.43 Å. There is one shorter (3.37 Å) and two longer (4.08 Å) Ba(2)-Br(2) bond lengths. In the third Ba site, Ba(3) is bonded in a 2-coordinate geometry to two equivalent O(1), two equivalent Br(2), and three equivalent Br(1) atoms. Both Ba(3)-O(1) bond lengths are 2.48 Å. There is one shorter (3.46 Å) and one longer (3.63 Å) Ba(3)-Br(2) bond length. There is one shorter (3.61 Å) and two longer (3.69 Å) Ba(3)-Br(1) bond lengths. O(1) is bonded to one Ba(2), one Ba(3), and two equivalent Ba(1) atoms to form OBa4 tetrahedra that share corners with two equivalent O(1)Ba4 tetrahedra, corners with four equivalent Br(1)Ba5 trigonal bipyramids, edges with three equivalent O(1)Ba4 tetrahedra, and  an edgeedge with one Br(1)Ba5 trigonal bipyramid. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to one Ba(1), one Ba(2), and three equivalent Ba(3) atoms to form distorted BrBa5 trigonal bipyramids that share corners with eight equivalent O(1)Ba4 tetrahedra, corners with two equivalent Br(1)Ba5 trigonal bipyramids, edges with two equivalent O(1)Ba4 tetrahedra, and edges with two equivalent Br(1)Ba5 trigonal bipyramids. In the second Br site, Br(2) is bonded in a 7-coordinate geometry to two equivalent Ba(1), two equivalent Ba(3), and three equivalent Ba(2) atoms.