(C3H2)3Cu3C31N3H6(O4Cl3)3 crystallizes in the trigonal R-3c space group. The structure consists of eighteen 2,3-dimethyl-1,3-butadiene molecules inside a Cu3C31N3H6(O4Cl3)3 framework. In each Cu3C31N3H6(O4Cl3)3 framework, Cu(1) is bonded in a T-shaped geometry to one N(1), one O(1), and one O(2) atom. The Cu(1)-N(1) bond length is 2.00 Å. The Cu(1)-O(1) bond length is 1.95 Å. The Cu(1)-O(2) bond length is 1.96 Å. There are eleven inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(2), one O(2), and one O(3) atom. The C(1)-C(2) bond length is 1.52 Å. The C(1)-O(2) bond length is 1.25 Å. The C(1)-O(3) bond length is 1.24 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(12), and one C(3) atom. The C(2)-C(12) bond length is 1.40 Å. The C(2)-C(3) bond length is 1.39 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(2), one C(4), and one Cl(2) atom. The C(3)-C(4) bond length is 1.40 Å. The C(3)-Cl(2) bond length is 1.73 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(13), one C(14), and one C(3) atom. The C(4)-C(13) bond length is 1.42 Å. The C(4)-C(14) bond length is 1.48 Å. In the fifth C site, C(5) is bonded in a distorted bent 120 degrees geometry to one N(1) and one H(1) atom. The C(5)-N(1) bond length is 1.32 Å. The C(5)-H(1) bond length is 0.94 Å. In the sixth C site, C(9) is bonded in a distorted bent 120 degrees geometry to one N(1) and one H(4) atom. The C(9)-N(1) bond length is 1.33 Å. The C(9)-H(4) bond length is 0.94 Å. In the seventh C site, C(10) is bonded in a distorted bent 120 degrees geometry to one C(11), one O(1), and one O(4) atom. The C(10)-C(11) bond length is 1.51 Å. The C(10)-O(1) bond length is 1.19 Å. The C(10)-O(4) bond length is 1.25 Å. In the eighth C site, C(11) is bonded in a trigonal planar geometry to one C(10), one C(12), and one C(13) atom. The C(11)-C(12) bond length is 1.39 Å. The C(11)-C(13) bond length is 1.39 Å. In the ninth C site, C(12) is bonded in a trigonal planar geometry to one C(11), one C(2), and one Cl(1) atom. The C(12)-Cl(1) bond length is 1.73 Å. In the tenth C site, C(13) is bonded in a distorted trigonal planar geometry to one C(11), one C(4), and one Cl(3) atom. The C(13)-Cl(3) bond length is 1.73 Å. In the eleventh C site, C(14) is bonded in a trigonal planar geometry to three equivalent C(4) atoms. N(1) is bonded in a trigonal planar geometry to one Cu(1), one C(5), and one C(9) atom. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(5) atom. In the second H site, H(4) is bonded in a single-bond geometry to one C(9) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Cu(1) and one C(10) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Cu(1) and one C(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to one C(1) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one C(10) atom. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a single-bond geometry to one C(12) atom. In the second Cl site, Cl(2) is bonded in a single-bond geometry to one C(3) atom. In the third Cl site, Cl(3) is bonded in a single-bond geometry to one C(13) atom. Linkers: 4 [O]C(=O)c1c(Cl)c([C](c2c(Cl)c(C([O])=O)c(Cl)c(C([O])=O)c2Cl)c2c(Cl)c(C([O])=O)c(Cl)c(C([O])=O)c2Cl)c(Cl)c(C([O])=O)c1Cl ,6 c1cc(-c2ccncc2)ccn1. Metal clusters: 12 O=[C]O[Cu]O[C]=O. The MOF has largest included sphere 5.30 A, density 1.38 g/cm3, surface area 3779.13 m2/g, accessible volume 0.33 cm3/g