(Bi3O4Br)4Br crystallizes in the monoclinic C2/m space group. The structure consists of two hydrogen bromide atoms inside a Bi3O4Br framework. In the Bi3O4Br framework, there are six inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to one O(1), one O(4), two equivalent O(3), and two equivalent Br(3) atoms. In the second Bi site, Bi(2) is bonded in a 7-coordinate geometry to one O(2), one O(5), one O(8), two equivalent O(6), and two equivalent O(7) atoms. In the third Bi site, Bi(3) is bonded in a 4-coordinate geometry to one O(4), one O(6), two equivalent O(8), and two equivalent Br(3) atoms. In the fourth Bi site, Bi(4) is bonded in a 4-coordinate geometry to one O(1), one O(7), two equivalent O(2), and two equivalent Br(1) atoms. In the fifth Bi site, Bi(5) is bonded in a 4-coordinate geometry to one O(6), three equivalent O(5), and two equivalent Br(1) atoms. In the sixth Bi site, Bi(6) is bonded in a body-centered cubic geometry to one O(2), one O(8), two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Bi(1), one Bi(4), and two equivalent Bi(6) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded to one Bi(2), one Bi(6), and two equivalent Bi(4) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded to two equivalent Bi(1) and two equivalent Bi(6) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fourth O site, O(4) is bonded to one Bi(1), one Bi(3), and two equivalent Bi(6) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fifth O site, O(5) is bonded to one Bi(2) and three equivalent Bi(5) atoms to form a mixture of distorted corner and edge-sharing OBi4 tetrahedra. In the sixth O site, O(6) is bonded to one Bi(3), one Bi(5), and two equivalent Bi(2) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Bi(4) and two equivalent Bi(2) atoms. In the eighth O site, O(8) is bonded to one Bi(2), one Bi(6), and two equivalent Bi(3) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 4-coordinate geometry to two equivalent Bi(4) and two equivalent Bi(5) atoms. In the second Br site, Br(3) is bonded in a 4-coordinate geometry to two equivalent Bi(1) and two equivalent Bi(3) atoms.
(Bi3O4Br)4Br crystallizes in the monoclinic C2/m space group. The structure consists of two hydrogen bromide atoms inside a Bi3O4Br framework. In the Bi3O4Br framework, there are six inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to one O(1), one O(4), two equivalent O(3), and two equivalent Br(3) atoms. The Bi(1)-O(1) bond length is 2.26 Å. The Bi(1)-O(4) bond length is 2.30 Å. Both Bi(1)-O(3) bond lengths are 2.28 Å. Both Bi(1)-Br(3) bond lengths are 3.45 Å. In the second Bi site, Bi(2) is bonded in a 7-coordinate geometry to one O(2), one O(5), one O(8), two equivalent O(6), and two equivalent O(7) atoms. The Bi(2)-O(2) bond length is 2.47 Å. The Bi(2)-O(5) bond length is 2.77 Å. The Bi(2)-O(8) bond length is 2.27 Å. Both Bi(2)-O(6) bond lengths are 2.55 Å. Both Bi(2)-O(7) bond lengths are 2.31 Å. In the third Bi site, Bi(3) is bonded in a 4-coordinate geometry to one O(4), one O(6), two equivalent O(8), and two equivalent Br(3) atoms. The Bi(3)-O(4) bond length is 2.31 Å. The Bi(3)-O(6) bond length is 2.25 Å. Both Bi(3)-O(8) bond lengths are 2.30 Å. Both Bi(3)-Br(3) bond lengths are 3.40 Å. In the fourth Bi site, Bi(4) is bonded in a 4-coordinate geometry to one O(1), one O(7), two equivalent O(2), and two equivalent Br(1) atoms. The Bi(4)-O(1) bond length is 2.36 Å. The Bi(4)-O(7) bond length is 2.15 Å. Both Bi(4)-O(2) bond lengths are 2.28 Å. Both Bi(4)-Br(1) bond lengths are 3.30 Å. In the fifth Bi site, Bi(5) is bonded in a 4-coordinate geometry to one O(6), three equivalent O(5), and two equivalent Br(1) atoms. The Bi(5)-O(6) bond length is 2.28 Å. There is one shorter (2.28 Å) and two longer (2.30 Å) Bi(5)-O(5) bond lengths. Both Bi(5)-Br(1) bond lengths are 3.31 Å. In the sixth Bi site, Bi(6) is bonded in a body-centered cubic geometry to one O(2), one O(8), two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. The Bi(6)-O(2) bond length is 2.38 Å. The Bi(6)-O(8) bond length is 2.63 Å. Both Bi(6)-O(1) bond lengths are 2.43 Å. There is one shorter (2.46 Å) and one longer (2.49 Å) Bi(6)-O(3) bond length. Both Bi(6)-O(4) bond lengths are 2.52 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Bi(1), one Bi(4), and two equivalent Bi(6) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded to one Bi(2), one Bi(6), and two equivalent Bi(4) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded to two equivalent Bi(1) and two equivalent Bi(6) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fourth O site, O(4) is bonded to one Bi(1), one Bi(3), and two equivalent Bi(6) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fifth O site, O(5) is bonded to one Bi(2) and three equivalent Bi(5) atoms to form a mixture of distorted corner and edge-sharing OBi4 tetrahedra. In the sixth O site, O(6) is bonded to one Bi(3), one Bi(5), and two equivalent Bi(2) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Bi(4) and two equivalent Bi(2) atoms. In the eighth O site, O(8) is bonded to one Bi(2), one Bi(6), and two equivalent Bi(3) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 4-coordinate geometry to two equivalent Bi(4) and two equivalent Bi(5) atoms. In the second Br site, Br(3) is bonded in a 4-coordinate geometry to two equivalent Bi(1) and two equivalent Bi(3) atoms.