Cu6C69N30H93Br crystallizes in the hexagonal P6_3/m space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a tetrahedral geometry to one C(11), one N(6), and two equivalent N(4) atoms. The Cu(1)-C(11) bond length is 1.87 Å. The Cu(1)-N(6) bond length is 2.06 Å. Both Cu(1)-N(4) bond lengths are 2.05 Å. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one N(5), two equivalent N(2), and one Br(1) atom. The Cu(2)-N(5) bond length is 1.92 Å. Both Cu(2)-N(2) bond lengths are 2.02 Å. The Cu(2)-Br(1) bond length is 2.63 Å. There are thirteen inequivalent C sites. In the first C site, C(11) is bonded in a linear geometry to one Cu(1) and one N(5) atom. The C(11)-N(5) bond length is 1.19 Å. In the second C site, C(12) is bonded in a distorted linear geometry to one C(13) and one N(6) atom. The C(12)-C(13) bond length is 1.53 Å. The C(12)-N(6) bond length is 1.09 Å. In the third C site, C(13) is bonded in a trigonal non-coplanar geometry to one C(12) and three equivalent H(15,16) atoms. All C(13)-H(15,16) bond lengths are 0.96 Å. In the fourth C site, C(1) is bonded in a trigonal planar geometry to one C(2), one C(4), and one C(5) atom. The C(1)-C(2) bond length is 1.37 Å. The C(1)-C(4) bond length is 1.43 Å. The C(1)-C(5) bond length is 1.48 Å. In the fifth C site, C(2) is bonded in a distorted trigonal planar geometry to one C(1), one C(3), and one N(3) atom. The C(2)-C(3) bond length is 1.48 Å. The C(2)-N(3) bond length is 1.35 Å. In the sixth C site, C(3) is bonded in a trigonal non-coplanar geometry to one C(2); one H(5); and two equivalent H(3,4) atoms. The C(3)-H(5) bond length is 0.96 Å. Both C(3)-H(3,4) bond lengths are 0.96 Å. In the seventh C site, C(4) is bonded in a distorted trigonal planar geometry to one C(1), one C(10), and one N(4) atom. The C(4)-C(10) bond length is 1.49 Å. The C(4)-N(4) bond length is 1.33 Å. In the eighth C site, C(5) is bonded in a trigonal planar geometry to one C(1), one C(6), and one C(7) atom. The C(5)-C(6) bond length is 1.39 Å. The C(5)-C(7) bond length is 1.42 Å. In the ninth C site, C(6) is bonded in a distorted trigonal planar geometry to one C(5), one C(8), and one N(1) atom. The C(6)-C(8) bond length is 1.48 Å. The C(6)-N(1) bond length is 1.35 Å. In the tenth C site, C(7) is bonded in a distorted trigonal planar geometry to one C(5), one C(9), and one N(2) atom. The C(7)-C(9) bond length is 1.49 Å. The C(7)-N(2) bond length is 1.34 Å. In the eleventh C site, C(8) is bonded in a trigonal non-coplanar geometry to one C(6), one H(6), one H(7), and one H(8) atom. The C(8)-H(6) bond length is 0.96 Å. The C(8)-H(7) bond length is 0.96 Å. The C(8)-H(8) bond length is 0.96 Å. In the twelfth C site, C(9) is bonded in a trigonal non-coplanar geometry to one C(7); one H(9); and two equivalent H(10,11) atoms. The C(9)-H(9) bond length is 0.96 Å. Both C(9)-H(10,11) bond lengths are 0.96 Å. In the thirteenth C site, C(10) is bonded in a trigonal non-coplanar geometry to one C(4); one H(13); and two equivalent H(12,14) atoms. The C(10)-H(13) bond length is 0.96 Å. Both C(10)-H(12,14) bond lengths are 0.96 Å. There are six inequivalent N sites. In the first N site, N(5) is bonded in a linear geometry to one Cu(2) and one C(11) atom. In the second N site, N(6) is bonded in a linear geometry to one Cu(1) and one C(12) atom. In the third N site, N(1) is bonded in a 2-coordinate geometry to one C(6), one N(2), and one H(1) atom. The N(1)-N(2) bond length is 1.35 Å. The N(1)-H(1) bond length is 0.86 Å. In the fourth N site, N(2) is bonded in a 3-coordinate geometry to one Cu(2), one C(7), and one N(1) atom. In the fifth N site, N(3) is bonded in a distorted bent 120 degrees geometry to one C(2), one N(4), and one H(2) atom. The N(3)-N(4) bond length is 1.38 Å. The N(3)-H(2) bond length is 0.86 Å. In the sixth N site, N(4) is bonded in a 3-coordinate geometry to one Cu(1), one C(4), and one N(3) atom. There are twelve inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one N(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one N(3) atom. In the third H site, H(3,4) is bonded in a single-bond geometry to one C(3) atom. In the fourth H site, H(5) is bonded in a single-bond geometry to one C(3) atom. In the fifth H site, H(6) is bonded in a single-bond geometry to one C(8) atom. In the sixth H site, H(7) is bonded in a single-bond geometry to one C(8) atom. In the seventh H site, H(8) is bonded in a single-bond geometry to one C(8) atom. In the eighth H site, H(9) is bonded in a single-bond geometry to one C(9) atom. In the ninth H site, H(10,11) is bonded in a single-bond geometry to one C(9) atom. In the tenth H site, H(12,14) is bonded in a single-bond geometry to one C(10) atom. In the eleventh H site, H(13) is bonded in a single-bond geometry to one C(10) atom. In the twelfth H site, H(15,16) is bonded in a single-bond geometry to one C(13) atom. Br(1) is bonded in a trigonal planar geometry to three equivalent Cu(2) atoms. Linkers: 12 Cc1n[nH]c(C)c1-c1c(C)n[nH]c1C. Metal clusters: 12 [Cu]. The MOF has largest included sphere 6.02 A, density 1.13 g/cm3, surface area 5420.46 m2/g, accessible volume 0.39 cm3/g