Ba4OBr6 crystallizes in the tetragonal P4_2/nmc space group. Ba(1) is bonded in a 7-coordinate geometry to one O(1), two equivalent Br(2), and four equivalent Br(1) atoms. O(1) is bonded to four equivalent Ba(1) atoms to form OBa4 tetrahedra that share corners with eight equivalent Br(1)Ba4 tetrahedra, corners with eight equivalent Br(2)Ba4 tetrahedra, and edges with four equivalent Br(1)Ba4 tetrahedra. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to four equivalent Ba(1) atoms to form distorted BrBa4 tetrahedra that share corners with two equivalent O(1)Ba4 tetrahedra, corners with four equivalent Br(2)Ba4 tetrahedra, corners with eight equivalent Br(1)Ba4 tetrahedra,  an edgeedge with one O(1)Ba4 tetrahedra, edges with two equivalent Br(1)Ba4 tetrahedra, and edges with two equivalent Br(2)Ba4 tetrahedra. In the second Br site, Br(2) is bonded to four equivalent Ba(1) atoms to form BrBa4 tetrahedra that share corners with four equivalent O(1)Ba4 tetrahedra, corners with eight equivalent Br(1)Ba4 tetrahedra, edges with two equivalent Br(2)Ba4 tetrahedra, and edges with four equivalent Br(1)Ba4 tetrahedra.
Ba4OBr6 crystallizes in the tetragonal P4_2/nmc space group. Ba(1) is bonded in a 7-coordinate geometry to one O(1), two equivalent Br(2), and four equivalent Br(1) atoms. The Ba(1)-O(1) bond length is 2.69 Å. There is one shorter (3.34 Å) and one longer (3.36 Å) Ba(1)-Br(2) bond length. There are two shorter (3.33 Å) and two longer (3.35 Å) Ba(1)-Br(1) bond lengths. O(1) is bonded to four equivalent Ba(1) atoms to form OBa4 tetrahedra that share corners with eight equivalent Br(1)Ba4 tetrahedra, corners with eight equivalent Br(2)Ba4 tetrahedra, and edges with four equivalent Br(1)Ba4 tetrahedra. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to four equivalent Ba(1) atoms to form distorted BrBa4 tetrahedra that share corners with two equivalent O(1)Ba4 tetrahedra, corners with four equivalent Br(2)Ba4 tetrahedra, corners with eight equivalent Br(1)Ba4 tetrahedra,  an edgeedge with one O(1)Ba4 tetrahedra, edges with two equivalent Br(1)Ba4 tetrahedra, and edges with two equivalent Br(2)Ba4 tetrahedra. In the second Br site, Br(2) is bonded to four equivalent Ba(1) atoms to form BrBa4 tetrahedra that share corners with four equivalent O(1)Ba4 tetrahedra, corners with eight equivalent Br(1)Ba4 tetrahedra, edges with two equivalent Br(2)Ba4 tetrahedra, and edges with four equivalent Br(1)Ba4 tetrahedra.