CsW3Br7 crystallizes in the trigonal P31c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to three equivalent Br(5) and three equivalent Br(6) atoms. In the second Cs site, Cs(2) is bonded to three equivalent Br(3), three equivalent Br(4), three equivalent Br(5), and three equivalent Br(6) atoms to form distorted CsBr12 cuboctahedra that share corners with three equivalent W(1)Br5 square pyramids, corners with three equivalent W(2)Br5 square pyramids, faces with three equivalent W(1)Br5 square pyramids, and faces with three equivalent W(2)Br5 square pyramids. There are two inequivalent W sites. In the first W site, W(1) is bonded to one Br(1), one Br(4), one Br(5), and two equivalent Br(3) atoms to form distorted WBr5 square pyramids that share  a cornercorner with one Cs(2)Br12 cuboctahedra, edges with two equivalent W(1)Br5 square pyramids, edges with two equivalent W(2)Br5 square pyramids, and  a faceface with one Cs(2)Br12 cuboctahedra. In the second W site, W(2) is bonded to one Br(2), one Br(3), one Br(6), and two equivalent Br(4) atoms to form distorted WBr5 square pyramids that share  a cornercorner with one Cs(2)Br12 cuboctahedra, edges with two equivalent W(1)Br5 square pyramids, edges with two equivalent W(2)Br5 square pyramids, and  a faceface with one Cs(2)Br12 cuboctahedra. There are six inequivalent Br sites. In the first Br site, Br(5) is bonded in a 3-coordinate geometry to one Cs(1), one Cs(2), and one W(1) atom. In the second Br site, Br(6) is bonded in a 3-coordinate geometry to one Cs(1), one Cs(2), and one W(2) atom. In the third Br site, Br(1) is bonded in a 3-coordinate geometry to three equivalent W(1) atoms. In the fourth Br site, Br(2) is bonded in a 3-coordinate geometry to three equivalent W(2) atoms. In the fifth Br site, Br(3) is bonded in a 4-coordinate geometry to one Cs(2), one W(2), and two equivalent W(1) atoms. In the sixth Br site, Br(4) is bonded in a 4-coordinate geometry to one Cs(2), one W(1), and two equivalent W(2) atoms.
CsW3Br7 crystallizes in the trigonal P31c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to three equivalent Br(5) and three equivalent Br(6) atoms. All Cs(1)-Br(5) bond lengths are 3.70 Å. All Cs(1)-Br(6) bond lengths are 3.68 Å. In the second Cs site, Cs(2) is bonded to three equivalent Br(3), three equivalent Br(4), three equivalent Br(5), and three equivalent Br(6) atoms to form distorted CsBr12 cuboctahedra that share corners with three equivalent W(1)Br5 square pyramids, corners with three equivalent W(2)Br5 square pyramids, faces with three equivalent W(1)Br5 square pyramids, and faces with three equivalent W(2)Br5 square pyramids. All Cs(2)-Br(3) bond lengths are 3.82 Å. All Cs(2)-Br(4) bond lengths are 3.86 Å. All Cs(2)-Br(5) bond lengths are 3.99 Å. All Cs(2)-Br(6) bond lengths are 4.15 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to one Br(1), one Br(4), one Br(5), and two equivalent Br(3) atoms to form distorted WBr5 square pyramids that share  a cornercorner with one Cs(2)Br12 cuboctahedra, edges with two equivalent W(1)Br5 square pyramids, edges with two equivalent W(2)Br5 square pyramids, and  a faceface with one Cs(2)Br12 cuboctahedra. The W(1)-Br(1) bond length is 2.64 Å. The W(1)-Br(4) bond length is 2.68 Å. The W(1)-Br(5) bond length is 2.61 Å. There is one shorter (2.64 Å) and one longer (2.67 Å) W(1)-Br(3) bond length. In the second W site, W(2) is bonded to one Br(2), one Br(3), one Br(6), and two equivalent Br(4) atoms to form distorted WBr5 square pyramids that share  a cornercorner with one Cs(2)Br12 cuboctahedra, edges with two equivalent W(1)Br5 square pyramids, edges with two equivalent W(2)Br5 square pyramids, and  a faceface with one Cs(2)Br12 cuboctahedra. The W(2)-Br(2) bond length is 2.64 Å. The W(2)-Br(3) bond length is 2.68 Å. The W(2)-Br(6) bond length is 2.61 Å. There is one shorter (2.64 Å) and one longer (2.67 Å) W(2)-Br(4) bond length. There are six inequivalent Br sites. In the first Br site, Br(5) is bonded in a 3-coordinate geometry to one Cs(1), one Cs(2), and one W(1) atom. In the second Br site, Br(6) is bonded in a 3-coordinate geometry to one Cs(1), one Cs(2), and one W(2) atom. In the third Br site, Br(1) is bonded in a 3-coordinate geometry to three equivalent W(1) atoms. In the fourth Br site, Br(2) is bonded in a 3-coordinate geometry to three equivalent W(2) atoms. In the fifth Br site, Br(3) is bonded in a 4-coordinate geometry to one Cs(2), one W(2), and two equivalent W(1) atoms. In the sixth Br site, Br(4) is bonded in a 4-coordinate geometry to one Cs(2), one W(1), and two equivalent W(2) atoms.