K3W2Cl9 crystallizes in the triclinic P1 space group. There are five inequivalent K sites. In the first K site, K(1) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(11), one Cl(14), one Cl(15), one Cl(17), one Cl(4), one Cl(5), one Cl(8), and one Cl(9) atom. In the second K site, K(2) is bonded in a 9-coordinate geometry to one Cl(10), one Cl(12), one Cl(13), one Cl(16), one Cl(18), one Cl(2), one Cl(3), one Cl(6), and one Cl(7) atom. In the third K site, K(3) is bonded in a 9-coordinate geometry to one Cl(12), one Cl(13), one Cl(16), one Cl(17), one Cl(2), one Cl(3), one Cl(6), one Cl(8), and one Cl(9) atom. In the fourth K site, K(4,5) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(10), one Cl(11), one Cl(14), one Cl(15), one Cl(18), one Cl(4), one Cl(5), and one Cl(7) atom. In the fifth K site, K(6) is bonded in a 9-coordinate geometry to one Cl(11), one Cl(14), one Cl(15), one Cl(17), one Cl(2), one Cl(3), one Cl(6), one Cl(8), and one Cl(9) atom. There are four inequivalent W sites. In the first W site, W(1) is bonded to one Cl(11), one Cl(14), one Cl(15), one Cl(17), one Cl(8), and one Cl(9) atom to form distorted face-sharing WCl6 octahedra. In the second W site, W(2) is bonded to one Cl(10), one Cl(12), one Cl(13), one Cl(16), one Cl(18), and one Cl(7) atom to form distorted face-sharing WCl6 octahedra. In the third W site, W(3) is bonded to one Cl(12), one Cl(13), one Cl(16), one Cl(2), one Cl(3), and one Cl(6) atom to form distorted face-sharing WCl6 octahedra. In the fourth W site, W(4) is bonded to one Cl(1), one Cl(11), one Cl(14), one Cl(15), one Cl(4), and one Cl(5) atom to form distorted face-sharing WCl6 octahedra. There are eighteen inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted see-saw-like geometry to one K(1); two equivalent K(4,5); and one W(4) atom. In the second Cl site, Cl(2) is bonded in a distorted see-saw-like geometry to one K(2), one K(3), one K(6), and one W(3) atom. In the third Cl site, Cl(3) is bonded in a distorted see-saw-like geometry to one K(2), one K(3), one K(6), and one W(3) atom. In the fourth Cl site, Cl(4) is bonded in a distorted see-saw-like geometry to one K(1); two equivalent K(4,5); and one W(4) atom. In the fifth Cl site, Cl(5) is bonded in a distorted see-saw-like geometry to one K(1); two equivalent K(4,5); and one W(4) atom. In the sixth Cl site, Cl(6) is bonded in a distorted see-saw-like geometry to one K(2), one K(3), one K(6), and one W(3) atom. In the seventh Cl site, Cl(7) is bonded in a distorted see-saw-like geometry to one K(2); two equivalent K(4,5); and one W(2) atom. In the eighth Cl site, Cl(8) is bonded in a distorted see-saw-like geometry to one K(1), one K(3), one K(6), and one W(1) atom. In the ninth Cl site, Cl(9) is bonded in a distorted see-saw-like geometry to one K(1), one K(3), one K(6), and one W(1) atom. In the tenth Cl site, Cl(10) is bonded in a distorted see-saw-like geometry to one K(2); two equivalent K(4,5); and one W(2) atom. In the eleventh Cl site, Cl(11) is bonded in a 5-coordinate geometry to one K(1); one K(4,5); one K(6); one W(1); and one W(4) atom. In the twelfth Cl site, Cl(12) is bonded in a 5-coordinate geometry to one K(2); one K(3); one K(4,5); one W(2); and one W(3) atom. In the thirteenth Cl site, Cl(13) is bonded in a 5-coordinate geometry to one K(2); one K(3); one K(4,5); one W(2); and one W(3) atom. In the fourteenth Cl site, Cl(14) is bonded in a 5-coordinate geometry to one K(1); one K(4,5); one K(6); one W(1); and one W(4) atom. In the fifteenth Cl site, Cl(15) is bonded in a 5-coordinate geometry to one K(1); one K(4,5); one K(6); one W(1); and one W(4) atom. In the sixteenth Cl site, Cl(16) is bonded in a 5-coordinate geometry to one K(2); one K(3); one K(4,5); one W(2); and one W(3) atom. In the seventeenth Cl site, Cl(17) is bonded in a distorted see-saw-like geometry to one K(1), one K(3), one K(6), and one W(1) atom. In the eighteenth Cl site, Cl(18) is bonded in a distorted see-saw-like geometry to one K(2); two equivalent K(4,5); and one W(2) atom.
K3W2Cl9 crystallizes in the triclinic P1 space group. There are five inequivalent K sites. In the first K site, K(1) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(11), one Cl(14), one Cl(15), one Cl(17), one Cl(4), one Cl(5), one Cl(8), and one Cl(9) atom. The K(1)-Cl(1) bond length is 3.42 Å. The K(1)-Cl(11) bond length is 3.16 Å. The K(1)-Cl(14) bond length is 3.16 Å. The K(1)-Cl(15) bond length is 3.16 Å. The K(1)-Cl(17) bond length is 3.42 Å. The K(1)-Cl(4) bond length is 3.43 Å. The K(1)-Cl(5) bond length is 3.42 Å. The K(1)-Cl(8) bond length is 3.42 Å. The K(1)-Cl(9) bond length is 3.43 Å. In the second K site, K(2) is bonded in a 9-coordinate geometry to one Cl(10), one Cl(12), one Cl(13), one Cl(16), one Cl(18), one Cl(2), one Cl(3), one Cl(6), and one Cl(7) atom. The K(2)-Cl(10) bond length is 3.42 Å. The K(2)-Cl(12) bond length is 3.16 Å. The K(2)-Cl(13) bond length is 3.16 Å. The K(2)-Cl(16) bond length is 3.16 Å. The K(2)-Cl(18) bond length is 3.43 Å. The K(2)-Cl(2) bond length is 3.43 Å. The K(2)-Cl(3) bond length is 3.42 Å. The K(2)-Cl(6) bond length is 3.43 Å. The K(2)-Cl(7) bond length is 3.43 Å. In the third K site, K(3) is bonded in a 9-coordinate geometry to one Cl(12), one Cl(13), one Cl(16), one Cl(17), one Cl(2), one Cl(3), one Cl(6), one Cl(8), and one Cl(9) atom. The K(3)-Cl(12) bond length is 3.62 Å. The K(3)-Cl(13) bond length is 3.62 Å. The K(3)-Cl(16) bond length is 3.62 Å. The K(3)-Cl(17) bond length is 3.33 Å. The K(3)-Cl(2) bond length is 3.22 Å. The K(3)-Cl(3) bond length is 3.22 Å. The K(3)-Cl(6) bond length is 3.22 Å. The K(3)-Cl(8) bond length is 3.33 Å. The K(3)-Cl(9) bond length is 3.33 Å. In the fourth K site, K(4,5) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(10), one Cl(11), one Cl(14), one Cl(15), one Cl(18), one Cl(4), one Cl(5), and one Cl(7) atom. The K(4,5)-Cl(1) bond length is 3.23 Å. The K(4,5)-Cl(10) bond length is 3.33 Å. The K(4,5)-Cl(11) bond length is 3.61 Å. The K(4,5)-Cl(14) bond length is 3.62 Å. The K(4,5)-Cl(15) bond length is 3.62 Å. The K(4,5)-Cl(18) bond length is 3.33 Å. The K(4,5)-Cl(4) bond length is 3.22 Å. The K(4,5)-Cl(5) bond length is 3.22 Å. The K(4,5)-Cl(7) bond length is 3.33 Å. In the fifth K site, K(6) is bonded in a 9-coordinate geometry to one Cl(11), one Cl(14), one Cl(15), one Cl(17), one Cl(2), one Cl(3), one Cl(6), one Cl(8), and one Cl(9) atom. The K(6)-Cl(11) bond length is 3.62 Å. The K(6)-Cl(14) bond length is 3.62 Å. The K(6)-Cl(15) bond length is 3.62 Å. The K(6)-Cl(17) bond length is 3.22 Å. The K(6)-Cl(2) bond length is 3.33 Å. The K(6)-Cl(3) bond length is 3.33 Å. The K(6)-Cl(6) bond length is 3.33 Å. The K(6)-Cl(8) bond length is 3.22 Å. The K(6)-Cl(9) bond length is 3.22 Å. There are four inequivalent W sites. In the first W site, W(1) is bonded to one Cl(11), one Cl(14), one Cl(15), one Cl(17), one Cl(8), and one Cl(9) atom to form distorted face-sharing WCl6 octahedra. The W(1)-Cl(11) bond length is 2.52 Å. The W(1)-Cl(14) bond length is 2.52 Å. The W(1)-Cl(15) bond length is 2.52 Å. The W(1)-Cl(17) bond length is 2.40 Å. The W(1)-Cl(8) bond length is 2.40 Å. The W(1)-Cl(9) bond length is 2.40 Å. In the second W site, W(2) is bonded to one Cl(10), one Cl(12), one Cl(13), one Cl(16), one Cl(18), and one Cl(7) atom to form distorted face-sharing WCl6 octahedra. The W(2)-Cl(10) bond length is 2.40 Å. The W(2)-Cl(12) bond length is 2.52 Å. The W(2)-Cl(13) bond length is 2.52 Å. The W(2)-Cl(16) bond length is 2.52 Å. The W(2)-Cl(18) bond length is 2.40 Å. The W(2)-Cl(7) bond length is 2.40 Å. In the third W site, W(3) is bonded to one Cl(12), one Cl(13), one Cl(16), one Cl(2), one Cl(3), and one Cl(6) atom to form distorted face-sharing WCl6 octahedra. The W(3)-Cl(12) bond length is 2.52 Å. The W(3)-Cl(13) bond length is 2.52 Å. The W(3)-Cl(16) bond length is 2.52 Å. The W(3)-Cl(2) bond length is 2.40 Å. The W(3)-Cl(3) bond length is 2.40 Å. The W(3)-Cl(6) bond length is 2.40 Å. In the fourth W site, W(4) is bonded to one Cl(1), one Cl(11), one Cl(14), one Cl(15), one Cl(4), and one Cl(5) atom to form distorted face-sharing WCl6 octahedra. The W(4)-Cl(1) bond length is 2.40 Å. The W(4)-Cl(11) bond length is 2.52 Å. The W(4)-Cl(14) bond length is 2.52 Å. The W(4)-Cl(15) bond length is 2.52 Å. The W(4)-Cl(4) bond length is 2.40 Å. The W(4)-Cl(5) bond length is 2.40 Å. There are eighteen inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted see-saw-like geometry to one K(1); two equivalent K(4,5); and one W(4) atom. In the second Cl site, Cl(2) is bonded in a distorted see-saw-like geometry to one K(2), one K(3), one K(6), and one W(3) atom. In the third Cl site, Cl(3) is bonded in a distorted see-saw-like geometry to one K(2), one K(3), one K(6), and one W(3) atom. In the fourth Cl site, Cl(4) is bonded in a distorted see-saw-like geometry to one K(1); two equivalent K(4,5); and one W(4) atom. In the fifth Cl site, Cl(5) is bonded in a distorted see-saw-like geometry to one K(1); two equivalent K(4,5); and one W(4) atom. In the sixth Cl site, Cl(6) is bonded in a distorted see-saw-like geometry to one K(2), one K(3), one K(6), and one W(3) atom. In the seventh Cl site, Cl(7) is bonded in a distorted see-saw-like geometry to one K(2); two equivalent K(4,5); and one W(2) atom. In the eighth Cl site, Cl(8) is bonded in a distorted see-saw-like geometry to one K(1), one K(3), one K(6), and one W(1) atom. In the ninth Cl site, Cl(9) is bonded in a distorted see-saw-like geometry to one K(1), one K(3), one K(6), and one W(1) atom. In the tenth Cl site, Cl(10) is bonded in a distorted see-saw-like geometry to one K(2); two equivalent K(4,5); and one W(2) atom. In the eleventh Cl site, Cl(11) is bonded in a 5-coordinate geometry to one K(1); one K(4,5); one K(6); one W(1); and one W(4) atom. In the twelfth Cl site, Cl(12) is bonded in a 5-coordinate geometry to one K(2); one K(3); one K(4,5); one W(2); and one W(3) atom. The Cl(12)-K(4,5) bond length is 3.62 Å. In the thirteenth Cl site, Cl(13) is bonded in a 5-coordinate geometry to one K(2); one K(3); one K(4,5); one W(2); and one W(3) atom. The Cl(13)-K(4,5) bond length is 3.61 Å. In the fourteenth Cl site, Cl(14) is bonded in a 5-coordinate geometry to one K(1); one K(4,5); one K(6); one W(1); and one W(4) atom. In the fifteenth Cl site, Cl(15) is bonded in a 5-coordinate geometry to one K(1); one K(4,5); one K(6); one W(1); and one W(4) atom. In the sixteenth Cl site, Cl(16) is bonded in a 5-coordinate geometry to one K(2); one K(3); one K(4,5); one W(2); and one W(3) atom. The Cl(16)-K(4,5) bond length is 3.62 Å. In the seventeenth Cl site, Cl(17) is bonded in a distorted see-saw-like geometry to one K(1), one K(3), one K(6), and one W(1) atom. In the eighteenth Cl site, Cl(18) is bonded in a distorted see-saw-like geometry to one K(2); two equivalent K(4,5); and one W(2) atom.