K2TeS3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form a mixture of edge and corner-sharing KS6 octahedra. The corner-sharing octahedral tilt angles range from 15-22°. In the second K site, K(2) is bonded to one S(1), two equivalent S(3), and three equivalent S(2) atoms to form a mixture of edge and corner-sharing KS6 octahedra. The corner-sharing octahedral tilt angles range from 15-21°. Te(1) is bonded in a trigonal non-coplanar geometry to one S(1), one S(2), and one S(3) atom. There are three inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one K(2), two equivalent K(1), and one Te(1) atom. In the second S site, S(2) is bonded to two equivalent K(1), three equivalent K(2), and one Te(1) atom to form distorted SK5Te octahedra that share corners with four equivalent S(2)K5Te octahedra,  a cornercorner with one S(3)K4Te trigonal bipyramid, edges with two equivalent S(2)K5Te octahedra, and edges with five equivalent S(3)K4Te trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-15°. In the third S site, S(3) is bonded to two equivalent K(1), two equivalent K(2), and one Te(1) atom to form SK4Te trigonal bipyramids that share  a cornercorner with one S(2)K5Te octahedra, corners with four equivalent S(3)K4Te trigonal bipyramids, and edges with five equivalent S(2)K5Te octahedra. The corner-sharing octahedral tilt angles are 19°.
K2TeS3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form a mixture of edge and corner-sharing KS6 octahedra. The corner-sharing octahedral tilt angles range from 15-22°. Both K(1)-S(1) bond lengths are 3.18 Å. There is one shorter (3.26 Å) and one longer (3.55 Å) K(1)-S(2) bond length. There is one shorter (3.25 Å) and one longer (3.27 Å) K(1)-S(3) bond length. In the second K site, K(2) is bonded to one S(1), two equivalent S(3), and three equivalent S(2) atoms to form a mixture of edge and corner-sharing KS6 octahedra. The corner-sharing octahedral tilt angles range from 15-21°. The K(2)-S(1) bond length is 3.16 Å. There is one shorter (3.19 Å) and one longer (3.25 Å) K(2)-S(3) bond length. There are a spread of K(2)-S(2) bond distances ranging from 3.22-3.30 Å. Te(1) is bonded in a trigonal non-coplanar geometry to one S(1), one S(2), and one S(3) atom. The Te(1)-S(1) bond length is 2.35 Å. The Te(1)-S(2) bond length is 2.37 Å. The Te(1)-S(3) bond length is 2.37 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one K(2), two equivalent K(1), and one Te(1) atom. In the second S site, S(2) is bonded to two equivalent K(1), three equivalent K(2), and one Te(1) atom to form distorted SK5Te octahedra that share corners with four equivalent S(2)K5Te octahedra,  a cornercorner with one S(3)K4Te trigonal bipyramid, edges with two equivalent S(2)K5Te octahedra, and edges with five equivalent S(3)K4Te trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-15°. In the third S site, S(3) is bonded to two equivalent K(1), two equivalent K(2), and one Te(1) atom to form SK4Te trigonal bipyramids that share  a cornercorner with one S(2)K5Te octahedra, corners with four equivalent S(3)K4Te trigonal bipyramids, and edges with five equivalent S(2)K5Te octahedra. The corner-sharing octahedral tilt angles are 19°.