CsW3I3Cl4 crystallizes in the trigonal P31c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a distorted hexagonal planar geometry to three equivalent I(1) and three equivalent I(2) atoms. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to three equivalent I(1), three equivalent I(2), and three equivalent Cl(4) atoms. There are two inequivalent W sites. In the first W site, W(1) is bonded to one I(1), one Cl(1), one Cl(3), and two equivalent Cl(4) atoms to form distorted edge-sharing WICl4 square pyramids. In the second W site, W(2) is bonded to one I(2), one Cl(2), one Cl(4), and two equivalent Cl(1) atoms to form distorted edge-sharing WICl4 square pyramids. There are two inequivalent I sites. In the first I site, I(1) is bonded in a 3-coordinate geometry to one Cs(1), one Cs(2), and one W(1) atom. In the second I site, I(2) is bonded in a distorted trigonal non-coplanar geometry to one Cs(1), one Cs(2), and one W(2) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(2) is bonded in a 3-coordinate geometry to three equivalent W(2) atoms. In the second Cl site, Cl(3) is bonded in a 3-coordinate geometry to three equivalent W(1) atoms. In the third Cl site, Cl(4) is bonded in a 4-coordinate geometry to one Cs(2), one W(2), and two equivalent W(1) atoms. In the fourth Cl site, Cl(1) is bonded in a 3-coordinate geometry to one W(1) and two equivalent W(2) atoms.
CsW3I3Cl4 crystallizes in the trigonal P31c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a distorted hexagonal planar geometry to three equivalent I(1) and three equivalent I(2) atoms. All Cs(1)-I(1) bond lengths are 3.92 Å. All Cs(1)-I(2) bond lengths are 3.84 Å. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to three equivalent I(1), three equivalent I(2), and three equivalent Cl(4) atoms. All Cs(2)-I(1) bond lengths are 4.34 Å. All Cs(2)-I(2) bond lengths are 4.09 Å. All Cs(2)-Cl(4) bond lengths are 4.00 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to one I(1), one Cl(1), one Cl(3), and two equivalent Cl(4) atoms to form distorted edge-sharing WICl4 square pyramids. The W(1)-I(1) bond length is 2.82 Å. The W(1)-Cl(1) bond length is 2.53 Å. The W(1)-Cl(3) bond length is 2.50 Å. There is one shorter (2.50 Å) and one longer (2.51 Å) W(1)-Cl(4) bond length. In the second W site, W(2) is bonded to one I(2), one Cl(2), one Cl(4), and two equivalent Cl(1) atoms to form distorted edge-sharing WICl4 square pyramids. The W(2)-I(2) bond length is 2.83 Å. The W(2)-Cl(2) bond length is 2.51 Å. The W(2)-Cl(4) bond length is 2.53 Å. There is one shorter (2.50 Å) and one longer (2.52 Å) W(2)-Cl(1) bond length. There are two inequivalent I sites. In the first I site, I(1) is bonded in a 3-coordinate geometry to one Cs(1), one Cs(2), and one W(1) atom. In the second I site, I(2) is bonded in a distorted trigonal non-coplanar geometry to one Cs(1), one Cs(2), and one W(2) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(2) is bonded in a 3-coordinate geometry to three equivalent W(2) atoms. In the second Cl site, Cl(3) is bonded in a 3-coordinate geometry to three equivalent W(1) atoms. In the third Cl site, Cl(4) is bonded in a 4-coordinate geometry to one Cs(2), one W(2), and two equivalent W(1) atoms. In the fourth Cl site, Cl(1) is bonded in a 3-coordinate geometry to one W(1) and two equivalent W(2) atoms.