CsW3Cl7 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 Cl(2) and three equivalent Cl(6) atoms. In the second Cs site, Cs(2) is bonded in a 12-coordinate geometry to three equivalent Cl(1), three equivalent Cl(2), three equivalent Cl(5), and three equivalent Cl(6) atoms. There are two inequivalent W sites. In the first W site, W(1) is bonded to one Cl(1), one Cl(2), one Cl(4), and two equivalent Cl(5) atoms to form distorted edge-sharing WCl5 square pyramids. In the second W site, W(2) is bonded to one Cl(3), one Cl(5), one Cl(6), and two equivalent Cl(1) atoms to form distorted edge-sharing WCl5 square pyramids. There are six inequivalent Cl sites. In the first Cl site, Cl(5) 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(6) is bonded in a 3-coordinate geometry to one Cs(1), one Cs(2), and one W(2) atom. In the third Cl site, Cl(1) is bonded in a 3-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 2-coordinate geometry to one Cs(1), one Cs(2), and one W(1) atom. In the fifth Cl site, Cl(3) is bonded in a 3-coordinate geometry to three equivalent W(2) atoms. In the sixth Cl site, Cl(4) is bonded in a 3-coordinate geometry to three equivalent W(1) atoms.
CsW3Cl7 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 Cl(2) and three equivalent Cl(6) atoms. All Cs(1)-Cl(2) bond lengths are 3.77 Å. All Cs(1)-Cl(6) bond lengths are 3.70 Å. In the second Cs site, Cs(2) is bonded in a 12-coordinate geometry to three equivalent Cl(1), three equivalent Cl(2), three equivalent Cl(5), and three equivalent Cl(6) atoms. All Cs(2)-Cl(1) bond lengths are 3.99 Å. All Cs(2)-Cl(2) bond lengths are 4.17 Å. All Cs(2)-Cl(5) bond lengths are 3.74 Å. All Cs(2)-Cl(6) bond lengths are 3.88 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to one Cl(1), one Cl(2), one Cl(4), and two equivalent Cl(5) atoms to form distorted edge-sharing WCl5 square pyramids. The W(1)-Cl(1) bond length is 2.54 Å. The W(1)-Cl(2) bond length is 2.44 Å. The W(1)-Cl(4) bond length is 2.51 Å. There is one shorter (2.51 Å) and one longer (2.53 Å) W(1)-Cl(5) bond length. In the second W site, W(2) is bonded to one Cl(3), one Cl(5), one Cl(6), and two equivalent Cl(1) atoms to form distorted edge-sharing WCl5 square pyramids. The W(2)-Cl(3) bond length is 2.52 Å. The W(2)-Cl(5) bond length is 2.54 Å. The W(2)-Cl(6) bond length is 2.45 Å. There is one shorter (2.51 Å) and one longer (2.53 Å) W(2)-Cl(1) bond length. There are six inequivalent Cl sites. In the first Cl site, Cl(5) 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(6) is bonded in a 3-coordinate geometry to one Cs(1), one Cs(2), and one W(2) atom. In the third Cl site, Cl(1) is bonded in a 3-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 2-coordinate geometry to one Cs(1), one Cs(2), and one W(1) atom. In the fifth Cl site, Cl(3) is bonded in a 3-coordinate geometry to three equivalent W(2) atoms. In the sixth Cl site, Cl(4) is bonded in a 3-coordinate geometry to three equivalent W(1) atoms.