Cu5C8H8(N4Br)3 crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a linear geometry to two equivalent Br(2) atoms. Both Cu(1)-Br(2) bond lengths are 2.28 Å. In the second Cu site, Cu(2) is bonded in a 2-coordinate geometry to one N(3), one N(6), and one Br(2) atom. The Cu(2)-N(3) bond length is 1.91 Å. The Cu(2)-N(6) bond length is 1.91 Å. The Cu(2)-Br(2) bond length is 2.73 Å. In the third Cu site, Cu(3) is bonded to two equivalent N(2), two equivalent N(4), and one Br(1) atom to form distorted corner-sharing CuBrN4 square pyramids. Both Cu(3)-N(2) bond lengths are 2.00 Å. Both Cu(3)-N(4) bond lengths are 2.01 Å. The Cu(3)-Br(1) bond length is 2.65 Å. In the fourth Cu site, Cu(4) is bonded to two equivalent N(1), two equivalent N(5), and one Br(1) atom to form corner-sharing CuBrN4 square pyramids. Both Cu(4)-N(1) bond lengths are 2.02 Å. Both Cu(4)-N(5) bond lengths are 2.03 Å. The Cu(4)-Br(1) bond length is 2.63 Å. There are four 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) 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) 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(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(2) bond length is 1.08 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one N(4), one N(6), and one H(3) atom. The C(3)-N(4) bond length is 1.33 Å. The C(3)-N(6) bond length is 1.36 Å. The C(3)-H(3) bond length is 1.08 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one N(5), one N(6), and one H(4) atom. The C(4)-N(5) bond length is 1.33 Å. The C(4)-N(6) bond length is 1.36 Å. The C(4)-H(4) bond length is 1.08 Å. There are six inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Cu(4), 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(3), 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(2), one C(1), and one C(2) atom. In the fourth N site, N(4) is bonded in a distorted trigonal planar geometry to one Cu(3), one C(3), and one N(5) atom. The N(4)-N(5) bond length is 1.36 Å. In the fifth N site, N(5) is bonded in a distorted trigonal planar geometry to one Cu(4), one C(4), and one N(4) atom. In the sixth N site, N(6) is bonded in a trigonal planar geometry to one Cu(2), one C(3), and one C(4) 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(3) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(4) atom. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in an L-shaped geometry to one Cu(3) and one Cu(4) atom. In the second Br site, Br(2) is bonded in a bent 120 degrees geometry to one Cu(1) and one Cu(2) atom. Linkers: 8 C1=NN=C[N]1. Metal clusters: 2 Br[Cu]Br.[Cu].[Cu] ,4 [Cu]. The MOF has largest included sphere 3.61 A, density 2.95 g/cm3, surface area 2530.23 m2/g, accessible volume 0.08 cm3/g