CuC5NH4S crystallizes in the monoclinic C2/c space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a trigonal planar geometry to one N(2) and two equivalent S(1) atoms. The Cu(1)-N(2) bond length is 1.97 Å. Both Cu(1)-S(1) bond lengths are 2.20 Å. In the second Cu site, Cu(2) is bonded to one N(1), one S(2), and two equivalent S(1) atoms to form a mixture of distorted edge and corner-sharing CuS3N tetrahedra. The Cu(2)-N(1) bond length is 2.02 Å. The Cu(2)-S(2) bond length is 2.28 Å. There is one shorter (2.30 Å) and one longer (2.36 Å) Cu(2)-S(1) bond length. There are eight inequivalent C sites. In the first 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 second 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 1.41 Å. The C(2)-H(2) bond length is 1.09 Å. In the third 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 1.41 Å. The C(3)-S(1) bond length is 1.75 Å. In the fourth 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)-C(5) bond length is 1.39 Å. The C(4)-H(3) bond length is 1.09 Å. In the fifth 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)-N(1) bond length is 1.35 Å. The C(5)-H(4) bond length is 1.09 Å. In the sixth C site, C(6) is bonded in a distorted bent 120 degrees geometry to one N(2) and one H(5) atom. The C(6)-N(2) bond length is 1.36 Å. The C(6)-H(5) bond length is 1.09 Å. In the seventh C site, C(7) is bonded in a distorted single-bond geometry to one C(8) and one H(6) atom. The C(7)-C(8) bond length is 1.41 Å. The C(7)-H(6) bond length is 1.09 Å. In the eighth C site, C(8) is bonded in a trigonal planar geometry to two equivalent C(7) and one S(2) atom. The C(8)-S(2) bond length is 1.74 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Cu(2), one C(1), and one C(5) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Cu(1) and two equivalent C(6) atoms. There are six 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. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(6) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(7) 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 a mixture of edge and corner-sharing SCu3C tetrahedra. In the second S site, S(2) is bonded in a distorted trigonal planar geometry to two equivalent Cu(2) and one C(8) atom. Linkers: 6 [S]c1ccncc1. Metal clusters: 6 [Cu]. The MOF has largest included sphere 2.68 A, density 2.09 g/cm3, surface area 3359.89 m2/g, accessible volume 0.11 cm3/g