Cu2C2N3H2Br2 crystallizes in the triclinic P-1 space group. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent N(1), two equivalent Br(1), and two equivalent Br(2) atoms to form distorted edge-sharing CuBr4N2 octahedra. Both Cu(1)-N(1) bond lengths are 1.94 Å. Both Cu(1)-Br(1) bond lengths are 2.62 Å. Both Cu(1)-Br(2) bond lengths are 2.93 Å. In the second Cu site, Cu(2) is bonded to two equivalent N(2), two equivalent Br(1), and two equivalent Br(2) atoms to form distorted edge-sharing CuBr4N2 octahedra. Both Cu(2)-N(2) bond lengths are 1.94 Å. Both Cu(2)-Br(1) bond lengths are 2.93 Å. Both Cu(2)-Br(2) bond lengths are 2.61 Å. In the third Cu site, Cu(3) is bonded in a 3-coordinate geometry to one N(3), one Br(1), and one Br(2) atom. The Cu(3)-N(3) bond length is 1.94 Å. The Cu(3)-Br(1) bond length is 2.37 Å. The Cu(3)-Br(2) bond length is 2.37 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one N(1); one N(3); and one H(1,2) atom. The C(1)-N(1) bond length is 1.33 Å. The C(1)-N(3) bond length is 1.36 Å. The C(1)-H(1,2) bond length is 1.08 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one N(2); one N(3); and one H(1,2) atom. The C(2)-N(2) bond length is 1.33 Å. The C(2)-N(3) bond length is 1.36 Å. The C(2)-H(1,2) bond length is 1.08 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Cu(1), one C(1), and one N(2) atom. The N(1)-N(2) bond length is 1.37 Å. In the second N site, N(2) is bonded in a distorted trigonal planar geometry to one Cu(2), one C(2), and one N(1) atom. In the third N site, N(3) is bonded in a trigonal planar geometry to one Cu(3), one C(1), and one C(2) atom. H(1,2) is bonded in a single-bond geometry to one C(1) atom. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one Cu(3) atom. In the second Br site, Br(2) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one Cu(3) atom. Linkers: 2 C1=NN=C[N]1. Metal clusters: 4 [Cu]. The MOF has largest included sphere 1.56 A, density 3.74 g/cm3, surface area 2064.17 m2/g, accessible volume 0.05 cm3/g