Cu2CN4HBr crystallizes in the orthorhombic Pbam space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent N(1) and two equivalent Br(1) atoms to form distorted edge-sharing CuBr2N2 tetrahedra. Both Cu(1)-N(1) bond lengths are 1.97 Å. Both Cu(1)-Br(1) bond lengths are 2.50 Å. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to two equivalent N(2) and two equivalent Br(1) atoms. Both Cu(2)-N(2) bond lengths are 1.92 Å. There is one shorter (2.60 Å) and one longer (2.83 Å) Cu(2)-Br(1) bond length. C(1) is bonded in a trigonal planar geometry to two equivalent N(2) and one H(1) atom. Both C(1)-N(2) bond lengths are 1.34 Å. The C(1)-H(1) bond length is 1.08 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Cu(1), one N(1), and one N(2) atom. The N(1)-N(1) bond length is 1.32 Å. The N(1)-N(2) bond length is 1.35 Å. In the second N site, N(2) is bonded in a 3-coordinate geometry to one Cu(2), one C(1), and one N(1) atom. H(1) is bonded in a single-bond geometry to one C(1) atom. Br(1) is bonded to two equivalent Cu(1) and two equivalent Cu(2) atoms to form a mixture of edge and corner-sharing BrCu4 tetrahedra. Linkers: 4 C1=NN=N[N]1. Metal clusters: 8 [Cu]. The MOF has largest included sphere 1.63 A, density 3.75 g/cm3, surface area 2043.34 m2/g, accessible volume 0.04 cm3/g