CuC3NH2S crystallizes in the orthorhombic Ama2 space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one N(1), one S(1), and two equivalent S(2) atoms to form corner-sharing CuS3N tetrahedra. The Cu(1)-N(1) bond length is 1.99 Å. The Cu(1)-S(1) bond length is 2.26 Å. Both Cu(1)-S(2) bond lengths are 2.31 Å. In the second Cu site, Cu(2) is bonded in a trigonal planar geometry to one N(2) and two equivalent S(1) atoms. The Cu(2)-N(2) bond length is 1.88 Å. Both Cu(2)-S(1) bond lengths are 2.23 Å. There are six inequivalent C sites. In the first C site, C(5) is bonded in a distorted trigonal planar geometry to one C(4), one N(1), and one H(4) atom. The C(5)-C(4) bond length is 1.39 Å. The C(5)-N(1) bond length is 1.35 Å. The C(5)-H(4) bond length is 1.09 Å. In the second C site, C(6) is bonded in a distorted single-bond geometry to one N(2) and one S(2) atom. The C(6)-N(2) bond length is 1.18 Å. The C(6)-S(2) bond length is 1.63 Å. In the third C site, C(1) is bonded in a distorted trigonal planar geometry to one C(2), one N(1), and one H(1) atom. The C(1)-C(2) bond length is 1.39 Å. The C(1)-N(1) bond length is 1.35 Å. The C(1)-H(1) bond length is 1.09 Å. In the fourth C site, C(2) is bonded in a distorted single-bond geometry to one C(1), one C(3), and one H(2) atom. The C(2)-C(3) bond length is 1.40 Å. The C(2)-H(2) bond length is 1.09 Å. In the fifth C site, C(3) is bonded in a trigonal planar geometry to one C(2), one C(4), and one S(1) atom. The C(3)-C(4) bond length is 1.40 Å. The C(3)-S(1) bond length is 1.77 Å. In the sixth C site, C(4) is bonded in a distorted single-bond geometry to one C(3), one C(5), and one H(3) atom. The C(4)-H(3) bond length is 1.09 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Cu(1), one C(1), and one C(5) atom. In the second N site, N(2) is bonded in a linear geometry to one Cu(2) and one C(6) atom. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(4) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(5) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Cu(1), two equivalent Cu(2), and one C(3) atom to form corner-sharing SCu3C tetrahedra. In the second S site, S(2) is bonded in a trigonal planar geometry to two equivalent Cu(1) and one C(6) atom. Linkers: 2 [S]c1ccncc1. Metal clusters: 4 [Cu]. The MOF has largest included sphere 1.64 A, density 2.52 g/cm3, surface area 2933.25 m2/g, accessible volume 0.08 cm3/g