Ba4OBr6 crystallizes in the orthorhombic P2_12_12_1 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a distorted single-bond geometry to one O(1), one Br(1), one Br(3), one Br(4), and two equivalent Br(2) atoms. In the second Ba site, Ba(2) is bonded in a distorted single-bond geometry to one O(1), one Br(3), one Br(5), two equivalent Br(1), and two equivalent Br(2) atoms. In the third Ba site, Ba(3) is bonded to one Br(1), one Br(3), one Br(4), and three equivalent Br(6) atoms to form a mixture of distorted corner and edge-sharing BaBr6 octahedra. The corner-sharing octahedral tilt angles are 30°. In the fourth Ba site, Ba(4) is bonded in a 1-coordinate geometry to one O(1), one Br(3), one Br(6), two equivalent Br(4), and two equivalent Br(5) atoms. O(1) is bonded in a trigonal planar geometry to one Ba(1), one Ba(2), and one Ba(4) atom. There are six inequivalent Br sites. In the first Br site, Br(1) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(3), and two equivalent Ba(2) atoms. In the second Br site, Br(2) is bonded in a rectangular see-saw-like geometry to two equivalent Ba(1) and two equivalent Ba(2) atoms. In the third Br site, Br(3) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), and one Ba(4) atom. In the fourth Br site, Br(4) is bonded to one Ba(1), one Ba(3), and two equivalent Ba(4) atoms to form a mixture of distorted corner and edge-sharing BrBa4 tetrahedra. In the fifth Br site, Br(5) is bonded in a distorted trigonal non-coplanar geometry to one Ba(2) and two equivalent Ba(4) atoms. In the sixth Br site, Br(6) is bonded to one Ba(4) and three equivalent Ba(3) atoms to form a mixture of distorted corner and edge-sharing BrBa4 trigonal pyramids.
Ba4OBr6 crystallizes in the orthorhombic P2_12_12_1 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a distorted single-bond geometry to one O(1), one Br(1), one Br(3), one Br(4), and two equivalent Br(2) atoms. The Ba(1)-O(1) bond length is 2.37 Å. The Ba(1)-Br(1) bond length is 3.71 Å. The Ba(1)-Br(3) bond length is 3.42 Å. The Ba(1)-Br(4) bond length is 3.37 Å. There is one shorter (3.43 Å) and one longer (3.51 Å) Ba(1)-Br(2) bond length. In the second Ba site, Ba(2) is bonded in a distorted single-bond geometry to one O(1), one Br(3), one Br(5), two equivalent Br(1), and two equivalent Br(2) atoms. The Ba(2)-O(1) bond length is 2.41 Å. The Ba(2)-Br(3) bond length is 3.51 Å. The Ba(2)-Br(5) bond length is 3.30 Å. There is one shorter (3.43 Å) and one longer (3.60 Å) Ba(2)-Br(1) bond length. There is one shorter (3.33 Å) and one longer (3.36 Å) Ba(2)-Br(2) bond length. In the third Ba site, Ba(3) is bonded to one Br(1), one Br(3), one Br(4), and three equivalent Br(6) atoms to form a mixture of distorted corner and edge-sharing BaBr6 octahedra. The corner-sharing octahedral tilt angles are 30°. The Ba(3)-Br(1) bond length is 3.22 Å. The Ba(3)-Br(3) bond length is 3.18 Å. The Ba(3)-Br(4) bond length is 3.28 Å. There are a spread of Ba(3)-Br(6) bond distances ranging from 3.26-3.38 Å. In the fourth Ba site, Ba(4) is bonded in a 1-coordinate geometry to one O(1), one Br(3), one Br(6), two equivalent Br(4), and two equivalent Br(5) atoms. The Ba(4)-O(1) bond length is 2.41 Å. The Ba(4)-Br(3) bond length is 3.58 Å. The Ba(4)-Br(6) bond length is 3.57 Å. Both Ba(4)-Br(4) bond lengths are 3.40 Å. There is one shorter (3.29 Å) and one longer (3.30 Å) Ba(4)-Br(5) bond length. O(1) is bonded in a trigonal planar geometry to one Ba(1), one Ba(2), and one Ba(4) atom. There are six inequivalent Br sites. In the first Br site, Br(1) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(3), and two equivalent Ba(2) atoms. In the second Br site, Br(2) is bonded in a rectangular see-saw-like geometry to two equivalent Ba(1) and two equivalent Ba(2) atoms. In the third Br site, Br(3) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), and one Ba(4) atom. In the fourth Br site, Br(4) is bonded to one Ba(1), one Ba(3), and two equivalent Ba(4) atoms to form a mixture of distorted corner and edge-sharing BrBa4 tetrahedra. In the fifth Br site, Br(5) is bonded in a distorted trigonal non-coplanar geometry to one Ba(2) and two equivalent Ba(4) atoms. In the sixth Br site, Br(6) is bonded to one Ba(4) and three equivalent Ba(3) atoms to form a mixture of distorted corner and edge-sharing BrBa4 trigonal pyramids.