Bi3O4Br crystallizes in the orthorhombic Pnna space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 3-coordinate geometry to one O(1), two equivalent O(2), and two equivalent Br(1) atoms. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Bi(1) and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Bi(2) and two equivalent Bi(1) atoms. Br(1) is bonded in a 4-coordinate geometry to four equivalent Bi(1) atoms.
Bi3O4Br crystallizes in the orthorhombic Pnna space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 3-coordinate geometry to one O(1), two equivalent O(2), and two equivalent Br(1) atoms. The Bi(1)-O(1) bond length is 2.11 Å. There is one shorter (2.13 Å) and one longer (2.14 Å) Bi(1)-O(2) bond length. There is one shorter (3.35 Å) and one longer (3.42 Å) Bi(1)-Br(1) bond length. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Both Bi(2)-O(2) bond lengths are 2.68 Å. There are two shorter (2.23 Å) and two longer (2.36 Å) Bi(2)-O(1) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Bi(1) and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Bi(2) and two equivalent Bi(1) atoms. Br(1) is bonded in a 4-coordinate geometry to four equivalent Bi(1) atoms.