CuC16H16S2Br crystallizes in the orthorhombic Pnma space group. Cu(1) is bonded to two equivalent S(1) and two equivalent Br(1) atoms to form corner-sharing CuS2Br2 tetrahedra. Both Cu(1)-S(1) bond lengths are 2.28 Å. There is one shorter (2.48 Å) and one longer (2.50 Å) Cu(1)-Br(1) bond length. There are eight inequivalent C sites. In the first C site, C(1) is bonded in a distorted single-bond geometry to one C(2), one C(6), and one H(1) atom. The C(1)-C(2) bond length is 1.40 Å. The C(1)-C(6) bond length is 1.40 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 C(8) atom. The C(3)-C(4) bond length is 1.40 Å. The C(3)-C(8) bond length is 1.50 Å. In the fourth C site, C(4) is bonded in a distorted single-bond geometry to one C(3) and one H(3) atom. The C(4)-H(3) bond length is 1.09 Å. In the fifth C site, C(5) is bonded in a distorted single-bond geometry to one C(6) and one H(4) atom. The C(5)-C(6) bond length is 1.40 Å. The C(5)-H(4) bond length is 1.09 Å. In the sixth C site, C(6) is bonded in a trigonal planar geometry to one C(1), one C(5), and one C(7) atom. The C(6)-C(7) bond length is 1.51 Å. In the seventh C site, C(7) is bonded in a distorted water-like geometry to one C(6), one H(5), one H(6), and one S(1) atom. The C(7)-H(5) bond length is 1.10 Å. The C(7)-H(6) bond length is 1.10 Å. The C(7)-S(1) bond length is 1.83 Å. In the eighth C site, C(8) is bonded in a distorted water-like geometry to one C(3), one H(7), one H(8), and one S(1) atom. The C(8)-H(7) bond length is 1.10 Å. The C(8)-H(8) bond length is 1.10 Å. The C(8)-S(1) bond length is 1.84 Å. There are eight 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(7) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(7) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(8) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(8) atom. S(1) is bonded in a trigonal non-coplanar geometry to one Cu(1), one C(7), and one C(8) atom. Br(1) is bonded in a water-like geometry to two equivalent Cu(1) atoms. Linkers: 4 c1cc2ccc1CSCc1ccc(cc1)CSC2. Metal clusters: 4 [Cu]. The MOF has largest included sphere 4.95 A, density 1.57 g/cm3, surface area 3880.59 m2/g, accessible volume 0.24 cm3/g