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) and three equivalent Br(1) atoms. In the second Ba site, Ba(2) is bonded in a 2-coordinate geometry to two equivalent O(1) and three equivalent Br(1) atoms. In the third Ba site, Ba(3) is bonded in a 6-coordinate geometry to two equivalent O(1), one Br(1), and three equivalent Br(2) atoms. O(1) is bonded to one Ba(2), one Ba(3), and two equivalent Ba(1) atoms to form a mixture of edge and corner-sharing OBa4 tetrahedra. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 7-coordinate geometry to one Ba(3), three equivalent Ba(1), and three equivalent Ba(2) atoms. In the second Br site, Br(2) is bonded in a distorted trigonal planar geometry to three equivalent Ba(3) 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) and three equivalent Br(1) atoms. There are two shorter (2.62 Å) and two longer (2.63 Å) Ba(1)-O(1) bond lengths. There is one shorter (3.63 Å) and two longer (3.84 Å) Ba(1)-Br(1) bond lengths. In the second Ba site, Ba(2) is bonded in a 2-coordinate geometry to two equivalent O(1) and three equivalent Br(1) atoms. Both Ba(2)-O(1) bond lengths are 2.41 Å. There is one shorter (3.42 Å) and two longer (3.93 Å) Ba(2)-Br(1) bond lengths. In the third Ba site, Ba(3) is bonded in a 6-coordinate geometry to two equivalent O(1), one Br(1), and three equivalent Br(2) atoms. Both Ba(3)-O(1) bond lengths are 2.44 Å. The Ba(3)-Br(1) bond length is 3.42 Å. There is one shorter (3.33 Å) and two longer (3.71 Å) Ba(3)-Br(2) bond lengths. O(1) is bonded to one Ba(2), one Ba(3), and two equivalent Ba(1) atoms to form a mixture of edge and corner-sharing OBa4 tetrahedra. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 7-coordinate geometry to one Ba(3), three equivalent Ba(1), and three equivalent Ba(2) atoms. In the second Br site, Br(2) is bonded in a distorted trigonal planar geometry to three equivalent Ba(3) atoms.