TlC3H2S crystallizes in the triclinic P-1 space group. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 3-coordinate geometry to one S(2) and two equivalent S(1) atoms. The Tl(1)-S(2) bond length is 3.19 Å. There is one shorter (3.09 Å) and one longer (3.19 Å) Tl(1)-S(1) bond length. In the second Tl site, Tl(2) is bonded in a distorted T-shaped geometry to one S(1) and two equivalent S(2) atoms. The Tl(2)-S(1) bond length is 3.15 Å. There is one shorter (3.10 Å) and one longer (3.19 Å) Tl(2)-S(2) bond length. There are six inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one C(2), one C(3), and one S(1) atom. The C(1)-C(2) bond length is 1.41 Å. The C(1)-C(3) bond length is 1.41 Å. The C(1)-S(1) bond length is 1.76 Å. In the second C site, C(2) is bonded in a distorted trigonal planar geometry to one C(1), one C(3), and one H(1) atom. The C(2)-C(3) bond length is 1.39 Å. The C(2)-H(1) bond length is 1.09 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(1), one C(2), and one H(2) atom. The C(3)-H(2) bond length is 1.09 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(5), one C(6), and one S(2) atom. The C(4)-C(5) bond length is 1.41 Å. The C(4)-C(6) bond length is 1.41 Å. The C(4)-S(2) bond length is 1.76 Å. In the fifth C site, C(5) is bonded in a distorted trigonal planar geometry to one C(4), one C(6), and one H(3) atom. The C(5)-C(6) bond length is 1.39 Å. The C(5)-H(3) bond length is 1.09 Å. In the sixth C site, C(6) is bonded in a distorted trigonal planar geometry to one C(4), one C(5), and one H(4) atom. The C(6)-H(4) bond length is 1.09 Å. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(3) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(5) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(6) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Tl(2), two equivalent Tl(1), and one C(1) atom to form distorted edge-sharing STl3C trigonal pyramids. In the second S site, S(2) is bonded in a distorted single-bond geometry to one Tl(1), two equivalent Tl(2), and one C(4) atom. Linkers: 2 [S]c1ccc([S])cc1. Metal clusters: 4 [Tl]. The MOF has largest included sphere 1.88 A, density 4.47 g/cm3, surface area 1272.78 m2/g, accessible volume 0.03 cm3/g