Bi(WBr3)3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent W sites. In the first W site, W(1) is bonded to one Br(1), one Br(2), one Br(3), one Br(4), and one Br(5) atom to form distorted WBr5 square pyramids that share  a cornercorner with one Bi(1)Br6 octahedra, edges with two equivalent W(2)Br5 square pyramids, and edges with two equivalent W(3)Br5 square pyramids. The corner-sharing octahedral tilt angles are 50°. In the second W site, W(2) is bonded to one Br(1), one Br(2), one Br(3), one Br(4), and one Br(6) atom to form distorted WBr5 square pyramids that share  a cornercorner with one Bi(1)Br6 octahedra, edges with two equivalent W(1)Br5 square pyramids, and edges with two equivalent W(3)Br5 square pyramids. The corner-sharing octahedral tilt angles are 43°. In the third W site, W(3) is bonded to one Br(1), one Br(2), one Br(3), one Br(4), and one Br(7) atom to form distorted WBr5 square pyramids that share  a cornercorner with one Bi(1)Br6 octahedra, edges with two equivalent W(1)Br5 square pyramids, and edges with two equivalent W(2)Br5 square pyramids. The corner-sharing octahedral tilt angles are 58°. Bi(1) is bonded to one Br(5), one Br(6), one Br(7), one Br(9), and two equivalent Br(8) atoms to form distorted BiBr6 octahedra that share  a cornercorner with one W(1)Br5 square pyramid,  a cornercorner with one W(2)Br5 square pyramid,  a cornercorner with one W(3)Br5 square pyramid, and  an edgeedge with one Bi(1)Br6 octahedra. There are nine inequivalent Br sites. In the first Br site, Br(5) is bonded in a bent 120 degrees geometry to one W(1) and one Bi(1) atom. In the second Br site, Br(6) is bonded in a distorted bent 150 degrees geometry to one W(2) and one Bi(1) atom. In the third Br site, Br(7) is bonded in a bent 120 degrees geometry to one W(3) and one Bi(1) atom. In the fourth Br site, Br(8) is bonded in a water-like geometry to two equivalent Bi(1) atoms. In the fifth Br site, Br(1) is bonded in a 3-coordinate geometry to one W(1), one W(2), and one W(3) atom. In the sixth Br site, Br(9) is bonded in a single-bond geometry to one Bi(1) atom. In the seventh Br site, Br(2) is bonded in a 3-coordinate geometry to one W(1), one W(2), and one W(3) atom. In the eighth Br site, Br(3) is bonded in a 3-coordinate geometry to one W(1), one W(2), and one W(3) atom. In the ninth Br site, Br(4) is bonded in a 3-coordinate geometry to one W(1), one W(2), and one W(3) atom.
Bi(WBr3)3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent W sites. In the first W site, W(1) is bonded to one Br(1), one Br(2), one Br(3), one Br(4), and one Br(5) atom to form distorted WBr5 square pyramids that share  a cornercorner with one Bi(1)Br6 octahedra, edges with two equivalent W(2)Br5 square pyramids, and edges with two equivalent W(3)Br5 square pyramids. The corner-sharing octahedral tilt angles are 50°. The W(1)-Br(1) bond length is 2.66 Å. The W(1)-Br(2) bond length is 2.62 Å. The W(1)-Br(3) bond length is 2.66 Å. The W(1)-Br(4) bond length is 2.65 Å. The W(1)-Br(5) bond length is 2.68 Å. In the second W site, W(2) is bonded to one Br(1), one Br(2), one Br(3), one Br(4), and one Br(6) atom to form distorted WBr5 square pyramids that share  a cornercorner with one Bi(1)Br6 octahedra, edges with two equivalent W(1)Br5 square pyramids, and edges with two equivalent W(3)Br5 square pyramids. The corner-sharing octahedral tilt angles are 43°. The W(2)-Br(1) bond length is 2.65 Å. The W(2)-Br(2) bond length is 2.65 Å. The W(2)-Br(3) bond length is 2.65 Å. The W(2)-Br(4) bond length is 2.65 Å. The W(2)-Br(6) bond length is 2.64 Å. In the third W site, W(3) is bonded to one Br(1), one Br(2), one Br(3), one Br(4), and one Br(7) atom to form distorted WBr5 square pyramids that share  a cornercorner with one Bi(1)Br6 octahedra, edges with two equivalent W(1)Br5 square pyramids, and edges with two equivalent W(2)Br5 square pyramids. The corner-sharing octahedral tilt angles are 58°. The W(3)-Br(1) bond length is 2.64 Å. The W(3)-Br(2) bond length is 2.63 Å. The W(3)-Br(3) bond length is 2.64 Å. The W(3)-Br(4) bond length is 2.65 Å. The W(3)-Br(7) bond length is 2.68 Å. Bi(1) is bonded to one Br(5), one Br(6), one Br(7), one Br(9), and two equivalent Br(8) atoms to form distorted BiBr6 octahedra that share  a cornercorner with one W(1)Br5 square pyramid,  a cornercorner with one W(2)Br5 square pyramid,  a cornercorner with one W(3)Br5 square pyramid, and  an edgeedge with one Bi(1)Br6 octahedra. The Bi(1)-Br(5) bond length is 3.03 Å. The Bi(1)-Br(6) bond length is 3.16 Å. The Bi(1)-Br(7) bond length is 2.94 Å. The Bi(1)-Br(9) bond length is 2.66 Å. There is one shorter (2.73 Å) and one longer (3.28 Å) Bi(1)-Br(8) bond length. There are nine inequivalent Br sites. In the first Br site, Br(5) is bonded in a bent 120 degrees geometry to one W(1) and one Bi(1) atom. In the second Br site, Br(6) is bonded in a distorted bent 150 degrees geometry to one W(2) and one Bi(1) atom. In the third Br site, Br(7) is bonded in a bent 120 degrees geometry to one W(3) and one Bi(1) atom. In the fourth Br site, Br(8) is bonded in a water-like geometry to two equivalent Bi(1) atoms. In the fifth Br site, Br(1) is bonded in a 3-coordinate geometry to one W(1), one W(2), and one W(3) atom. In the sixth Br site, Br(9) is bonded in a single-bond geometry to one Bi(1) atom. In the seventh Br site, Br(2) is bonded in a 3-coordinate geometry to one W(1), one W(2), and one W(3) atom. In the eighth Br site, Br(3) is bonded in a 3-coordinate geometry to one W(1), one W(2), and one W(3) atom. In the ninth Br site, Br(4) is bonded in a 3-coordinate geometry to one W(1), one W(2), and one W(3) atom.