Cu2C5NH4SBr crystallizes in the monoclinic Pc space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a trigonal planar geometry to two equivalent S(1) and one Br(1) atom. There is one shorter (2.19 Å) and one longer (2.20 Å) Cu(1)-S(1) bond length. The Cu(1)-Br(1) bond length is 2.39 Å. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one N(1), one S(1), and two equivalent Br(1) atoms. The Cu(2)-N(1) bond length is 1.98 Å. The Cu(2)-S(1) bond length is 2.21 Å. There is one shorter (2.50 Å) and one longer (2.65 Å) Cu(2)-Br(1) bond length. There are five 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 1.38 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 1.40 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 1.40 Å. The C(3)-S(1) bond length is 1.77 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. N(1) is bonded in a trigonal planar geometry to one Cu(2), one C(1), and one C(5) 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. S(1) is bonded to one Cu(2), two equivalent Cu(1), and one C(3) atom to form corner-sharing SCu3C tetrahedra. Br(1) is bonded in a trigonal non-coplanar geometry to one Cu(1) and two equivalent Cu(2) atoms. Linkers: 2 [S]c1ccncc1. Metal clusters: 4 [Cu]. The MOF has largest included sphere 1.46 A, density 3.00 g/cm3, surface area 2484.79 m2/g, accessible volume 0.06 cm3/g