Cu2C3N3H3Br2 crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one N(2) and three equivalent Br(1) atoms to form corner-sharing CuBr3N tetrahedra. The Cu(1)-N(2) bond length is 1.98 Å. There is one shorter (2.40 Å) and two longer (2.49 Å) Cu(1)-Br(1) bond lengths. In the second Cu site, Cu(2) is bonded to two equivalent N(1) and two equivalent Br(2) atoms to form distorted corner-sharing CuBr2N2 tetrahedra. Both Cu(2)-N(1) bond lengths are 2.00 Å. There is one shorter (2.42 Å) and one longer (2.54 Å) Cu(2)-Br(2) bond length. There are two inequivalent C sites. In the first C site, C(2) is bonded in a trigonal planar geometry to two equivalent N(1) and one H(2) atom. Both C(2)-N(1) bond lengths are 1.34 Å. The C(2)-H(2) bond length is 1.09 Å. In the second C site, C(1) is bonded in a trigonal planar geometry to one N(1), one N(2), and one H(1) atom. The C(1)-N(1) bond length is 1.34 Å. The C(1)-N(2) bond length is 1.35 Å. The C(1)-H(1) bond length is 1.09 Å. There are two inequivalent N sites. In the first N site, N(2) is bonded in a trigonal planar geometry to one Cu(1) and two equivalent C(1) atoms. In the second N site, N(1) is bonded in a trigonal planar geometry to one Cu(2), one C(1), and one C(2) atom. There are two 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. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a trigonal non-coplanar geometry to three equivalent Cu(1) atoms. In the second Br site, Br(2) is bonded in an L-shaped geometry to two equivalent Cu(2) atoms. Linkers: 6 C1=NC=[N]=C[N]1. Metal clusters: 12 [Cu]. The MOF has largest included sphere 2.72 A, density 3.33 g/cm3, surface area 2230.84 m2/g, accessible volume 0.06 cm3/g