CsW3Br3Cl4 crystallizes in the trigonal P31c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to three equivalent Br(1) and three equivalent Br(2) atoms to form distorted CsBr6 octahedra that share corners with six equivalent Cs(2)Br6Cl6 cuboctahedra, corners with three equivalent W(1)BrCl4 square pyramids, and corners with three equivalent W(2)BrCl4 square pyramids. In the second Cs site, Cs(2) is bonded to three equivalent Br(1), three equivalent Br(2), three equivalent Cl(1), and three equivalent Cl(3) atoms to form distorted CsBr6Cl6 cuboctahedra that share corners with six equivalent Cs(1)Br6 octahedra, corners with three equivalent W(1)BrCl4 square pyramids, corners with three equivalent W(2)BrCl4 square pyramids, faces with three equivalent W(1)BrCl4 square pyramids, and faces with three equivalent W(2)BrCl4 square pyramids. The corner-sharing octahedral tilt angles range from 44-49°. There are two inequivalent W sites. In the first W site, W(1) is bonded to one Br(2), one Cl(1), one Cl(4), and two equivalent Cl(3) atoms to form WBrCl4 square pyramids that share  a cornercorner with one Cs(2)Br6Cl6 cuboctahedra,  a cornercorner with one Cs(1)Br6 octahedra, edges with two equivalent W(1)BrCl4 square pyramids, edges with two equivalent W(2)BrCl4 square pyramids, and  a faceface with one Cs(2)Br6Cl6 cuboctahedra. The corner-sharing octahedral tilt angles are 64°. In the second W site, W(2) is bonded to one Br(1), one Cl(2), one Cl(3), and two equivalent Cl(1) atoms to form WBrCl4 square pyramids that share  a cornercorner with one Cs(2)Br6Cl6 cuboctahedra,  a cornercorner with one Cs(1)Br6 octahedra, edges with two equivalent W(1)BrCl4 square pyramids, edges with two equivalent W(2)BrCl4 square pyramids, and  a faceface with one Cs(2)Br6Cl6 cuboctahedra. The corner-sharing octahedral tilt angles are 54°. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 2-coordinate geometry to one Cs(1), one Cs(2), and one W(2) atom. In the second Br site, Br(2) is bonded in a 3-coordinate geometry to one Cs(1), one Cs(2), and one W(1) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(3) is bonded in a 4-coordinate geometry to one Cs(2), one W(2), and two equivalent W(1) atoms. In the second Cl site, Cl(4) is bonded in a 3-coordinate geometry to three equivalent W(1) atoms. In the third Cl site, Cl(1) is bonded in a 4-coordinate geometry to one Cs(2), one W(1), and two equivalent W(2) atoms. In the fourth Cl site, Cl(2) is bonded in a 3-coordinate geometry to three equivalent W(2) atoms.
CsW3Br3Cl4 crystallizes in the trigonal P31c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to three equivalent Br(1) and three equivalent Br(2) atoms to form distorted CsBr6 octahedra that share corners with six equivalent Cs(2)Br6Cl6 cuboctahedra, corners with three equivalent W(1)BrCl4 square pyramids, and corners with three equivalent W(2)BrCl4 square pyramids. All Cs(1)-Br(1) bond lengths are 3.73 Å. All Cs(1)-Br(2) bond lengths are 3.74 Å. In the second Cs site, Cs(2) is bonded to three equivalent Br(1), three equivalent Br(2), three equivalent Cl(1), and three equivalent Cl(3) atoms to form distorted CsBr6Cl6 cuboctahedra that share corners with six equivalent Cs(1)Br6 octahedra, corners with three equivalent W(1)BrCl4 square pyramids, corners with three equivalent W(2)BrCl4 square pyramids, faces with three equivalent W(1)BrCl4 square pyramids, and faces with three equivalent W(2)BrCl4 square pyramids. The corner-sharing octahedral tilt angles range from 44-49°. All Cs(2)-Br(1) bond lengths are 4.23 Å. All Cs(2)-Br(2) bond lengths are 3.92 Å. All Cs(2)-Cl(1) bond lengths are 3.84 Å. All Cs(2)-Cl(3) bond lengths are 3.99 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to one Br(2), one Cl(1), one Cl(4), and two equivalent Cl(3) atoms to form WBrCl4 square pyramids that share  a cornercorner with one Cs(2)Br6Cl6 cuboctahedra,  a cornercorner with one Cs(1)Br6 octahedra, edges with two equivalent W(1)BrCl4 square pyramids, edges with two equivalent W(2)BrCl4 square pyramids, and  a faceface with one Cs(2)Br6Cl6 cuboctahedra. The corner-sharing octahedral tilt angles are 64°. The W(1)-Br(2) bond length is 2.61 Å. The W(1)-Cl(1) bond length is 2.53 Å. The W(1)-Cl(4) bond length is 2.51 Å. There is one shorter (2.51 Å) and one longer (2.52 Å) W(1)-Cl(3) bond length. In the second W site, W(2) is bonded to one Br(1), one Cl(2), one Cl(3), and two equivalent Cl(1) atoms to form WBrCl4 square pyramids that share  a cornercorner with one Cs(2)Br6Cl6 cuboctahedra,  a cornercorner with one Cs(1)Br6 octahedra, edges with two equivalent W(1)BrCl4 square pyramids, edges with two equivalent W(2)BrCl4 square pyramids, and  a faceface with one Cs(2)Br6Cl6 cuboctahedra. The corner-sharing octahedral tilt angles are 54°. The W(2)-Br(1) bond length is 2.61 Å. The W(2)-Cl(2) bond length is 2.51 Å. The W(2)-Cl(3) bond length is 2.53 Å. There is one shorter (2.51 Å) and one longer (2.52 Å) W(2)-Cl(1) bond length. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 2-coordinate geometry to one Cs(1), one Cs(2), and one W(2) atom. In the second Br site, Br(2) is bonded in a 3-coordinate geometry to one Cs(1), one Cs(2), and one W(1) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(3) is bonded in a 4-coordinate geometry to one Cs(2), one W(2), and two equivalent W(1) atoms. In the second Cl site, Cl(4) is bonded in a 3-coordinate geometry to three equivalent W(1) atoms. In the third Cl site, Cl(1) is bonded in a 4-coordinate geometry to one Cs(2), one W(1), and two equivalent W(2) atoms. In the fourth Cl site, Cl(2) is bonded in a 3-coordinate geometry to three equivalent W(2) atoms.