Cs2TeS3 crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to one Te(2), one S(1), one S(4), one S(6), two equivalent S(2), and two equivalent S(3) atoms. In the second Cs site, Cs(2) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(6), and two equivalent S(5) atoms. In the third Cs site, Cs(3) is bonded to one S(1), one S(2), one S(3), one S(5), one S(6), and two equivalent S(4) atoms to form distorted edge-sharing CsS7 pentagonal bipyramids. In the fourth Cs site, Cs(4) is bonded in a 7-coordinate geometry to one S(2), one S(3), one S(4), one S(6), two equivalent S(1), and two equivalent S(5) atoms. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded in a trigonal non-coplanar geometry to one S(1), one S(2), and one S(3) atom. In the second Te site, Te(2) is bonded in a distorted trigonal non-coplanar geometry to one Cs(1), one S(4), one S(5), and one S(6) atom. There are six inequivalent S sites. In the first S site, S(3) is bonded in a 6-coordinate geometry to one Cs(2), one Cs(3), one Cs(4), two equivalent Cs(1), and one Te(1) atom. In the second S site, S(4) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), one Cs(4), two equivalent Cs(3), and one Te(2) atom. In the third S site, S(5) is bonded in a 6-coordinate geometry to one Cs(3), two equivalent Cs(2), two equivalent Cs(4), and one Te(2) atom. In the fourth S site, S(6) is bonded in a 5-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), one Cs(4), and one Te(2) atom. In the fifth S site, S(1) is bonded to one Cs(1), one Cs(2), one Cs(3), two equivalent Cs(4), and one Te(1) atom to form a mixture of distorted corner and face-sharing SCs5Te octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the sixth S site, S(2) is bonded to one Cs(2), one Cs(3), one Cs(4), two equivalent Cs(1), and one Te(1) atom to form a mixture of distorted corner, face, and edge-sharing SCs5Te octahedra. The corner-sharing octahedral tilt angles are 44°.
Cs2TeS3 crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to one Te(2), one S(1), one S(4), one S(6), two equivalent S(2), and two equivalent S(3) atoms. The Cs(1)-Te(2) bond length is 4.11 Å. The Cs(1)-S(1) bond length is 3.75 Å. The Cs(1)-S(4) bond length is 3.63 Å. The Cs(1)-S(6) bond length is 3.60 Å. There is one shorter (3.52 Å) and one longer (3.72 Å) Cs(1)-S(2) bond length. There is one shorter (3.84 Å) and one longer (3.86 Å) Cs(1)-S(3) bond length. In the second Cs site, Cs(2) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(6), and two equivalent S(5) atoms. The Cs(2)-S(1) bond length is 3.57 Å. The Cs(2)-S(2) bond length is 3.56 Å. The Cs(2)-S(3) bond length is 3.68 Å. The Cs(2)-S(4) bond length is 4.07 Å. The Cs(2)-S(6) bond length is 3.92 Å. There is one shorter (3.77 Å) and one longer (3.84 Å) Cs(2)-S(5) bond length. In the third Cs site, Cs(3) is bonded to one S(1), one S(2), one S(3), one S(5), one S(6), and two equivalent S(4) atoms to form distorted edge-sharing CsS7 pentagonal bipyramids. The Cs(3)-S(1) bond length is 3.57 Å. The Cs(3)-S(2) bond length is 3.77 Å. The Cs(3)-S(3) bond length is 3.78 Å. The Cs(3)-S(5) bond length is 3.82 Å. The Cs(3)-S(6) bond length is 3.69 Å. There is one shorter (3.90 Å) and one longer (3.91 Å) Cs(3)-S(4) bond length. In the fourth Cs site, Cs(4) is bonded in a 7-coordinate geometry to one S(2), one S(3), one S(4), one S(6), two equivalent S(1), and two equivalent S(5) atoms. The Cs(4)-S(2) bond length is 3.54 Å. The Cs(4)-S(3) bond length is 3.79 Å. The Cs(4)-S(4) bond length is 3.63 Å. The Cs(4)-S(6) bond length is 3.73 Å. There is one shorter (3.62 Å) and one longer (3.66 Å) Cs(4)-S(1) bond length. There is one shorter (3.73 Å) and one longer (4.14 Å) Cs(4)-S(5) bond length. There are two inequivalent Te sites. In the first Te site, 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 2.37 Å. The Te(1)-S(2) bond length is 2.37 Å. The Te(1)-S(3) bond length is 2.37 Å. In the second Te site, Te(2) is bonded in a distorted trigonal non-coplanar geometry to one Cs(1), one S(4), one S(5), and one S(6) atom. The Te(2)-S(4) bond length is 2.37 Å. The Te(2)-S(5) bond length is 2.37 Å. The Te(2)-S(6) bond length is 2.36 Å. There are six inequivalent S sites. In the first S site, S(3) is bonded in a 6-coordinate geometry to one Cs(2), one Cs(3), one Cs(4), two equivalent Cs(1), and one Te(1) atom. In the second S site, S(4) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), one Cs(4), two equivalent Cs(3), and one Te(2) atom. In the third S site, S(5) is bonded in a 6-coordinate geometry to one Cs(3), two equivalent Cs(2), two equivalent Cs(4), and one Te(2) atom. In the fourth S site, S(6) is bonded in a 5-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), one Cs(4), and one Te(2) atom. In the fifth S site, S(1) is bonded to one Cs(1), one Cs(2), one Cs(3), two equivalent Cs(4), and one Te(1) atom to form a mixture of distorted corner and face-sharing SCs5Te octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the sixth S site, S(2) is bonded to one Cs(2), one Cs(3), one Cs(4), two equivalent Cs(1), and one Te(1) atom to form a mixture of distorted corner, face, and edge-sharing SCs5Te octahedra. The corner-sharing octahedral tilt angles are 44°.