K3WS3OCl crystallizes in the orthorhombic Pca2_1 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(2), one O(1), and two equivalent Cl(1) atoms. In the second K site, K(2) is bonded in a 7-coordinate geometry to two equivalent S(2), two equivalent S(3), one O(1), and two equivalent Cl(1) atoms. In the third K site, K(3) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(3), one O(1), and two equivalent Cl(1) atoms. W(1) is bonded in a distorted tetrahedral geometry to one S(1), one S(2), one S(3), and one O(1) atom. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent K(1), two equivalent K(3), and one W(1) atom to form distorted SK4W trigonal bipyramids that share corners with three equivalent S(2)K4W trigonal bipyramids, corners with four equivalent S(1)K4W trigonal bipyramids, edges with four equivalent Cl(1)K6 octahedra, and  an edgeedge with one S(2)K4W trigonal bipyramid. In the second S site, S(2) is bonded to two equivalent K(1), two equivalent K(2), and one W(1) atom to form distorted SK4W trigonal bipyramids that share corners with three equivalent S(1)K4W trigonal bipyramids, corners with four equivalent S(2)K4W trigonal bipyramids, edges with four equivalent Cl(1)K6 octahedra, and  an edgeedge with one S(1)K4W trigonal bipyramid. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent K(2), two equivalent K(3), and one W(1) atom. O(1) is bonded in a distorted rectangular see-saw-like geometry to one K(1), one K(2), one K(3), and one W(1) atom. Cl(1) is bonded to two equivalent K(1), two equivalent K(2), and two equivalent K(3) atoms to form ClK6 octahedra that share corners with six equivalent Cl(1)K6 octahedra, edges with four equivalent S(1)K4W trigonal bipyramids, and edges with four equivalent S(2)K4W trigonal bipyramids. The corner-sharing octahedral tilt angles range from 14-20°.
K3WS3OCl crystallizes in the orthorhombic Pca2_1 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(2), one O(1), and two equivalent Cl(1) atoms. There is one shorter (3.38 Å) and one longer (3.45 Å) K(1)-S(1) bond length. There is one shorter (3.41 Å) and one longer (3.43 Å) K(1)-S(2) bond length. The K(1)-O(1) bond length is 2.88 Å. There is one shorter (3.19 Å) and one longer (3.21 Å) K(1)-Cl(1) bond length. In the second K site, K(2) is bonded in a 7-coordinate geometry to two equivalent S(2), two equivalent S(3), one O(1), and two equivalent Cl(1) atoms. There is one shorter (3.33 Å) and one longer (3.42 Å) K(2)-S(2) bond length. There is one shorter (3.40 Å) and one longer (3.43 Å) K(2)-S(3) bond length. The K(2)-O(1) bond length is 2.78 Å. There is one shorter (3.16 Å) and one longer (3.33 Å) K(2)-Cl(1) bond length. In the third K site, K(3) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(3), one O(1), and two equivalent Cl(1) atoms. There is one shorter (3.30 Å) and one longer (3.44 Å) K(3)-S(1) bond length. There is one shorter (3.41 Å) and one longer (3.43 Å) K(3)-S(3) bond length. The K(3)-O(1) bond length is 2.90 Å. There is one shorter (3.23 Å) and one longer (3.25 Å) K(3)-Cl(1) bond length. W(1) is bonded in a distorted tetrahedral geometry to one S(1), one S(2), one S(3), and one O(1) atom. The W(1)-S(1) bond length is 2.24 Å. The W(1)-S(2) bond length is 2.24 Å. The W(1)-S(3) bond length is 2.24 Å. The W(1)-O(1) bond length is 1.79 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent K(1), two equivalent K(3), and one W(1) atom to form distorted SK4W trigonal bipyramids that share corners with three equivalent S(2)K4W trigonal bipyramids, corners with four equivalent S(1)K4W trigonal bipyramids, edges with four equivalent Cl(1)K6 octahedra, and  an edgeedge with one S(2)K4W trigonal bipyramid. In the second S site, S(2) is bonded to two equivalent K(1), two equivalent K(2), and one W(1) atom to form distorted SK4W trigonal bipyramids that share corners with three equivalent S(1)K4W trigonal bipyramids, corners with four equivalent S(2)K4W trigonal bipyramids, edges with four equivalent Cl(1)K6 octahedra, and  an edgeedge with one S(1)K4W trigonal bipyramid. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent K(2), two equivalent K(3), and one W(1) atom. O(1) is bonded in a distorted rectangular see-saw-like geometry to one K(1), one K(2), one K(3), and one W(1) atom. Cl(1) is bonded to two equivalent K(1), two equivalent K(2), and two equivalent K(3) atoms to form ClK6 octahedra that share corners with six equivalent Cl(1)K6 octahedra, edges with four equivalent S(1)K4W trigonal bipyramids, and edges with four equivalent S(2)K4W trigonal bipyramids. The corner-sharing octahedral tilt angles range from 14-20°.