WCu4C16H16(N2S)4WCu4C28S4(NI)4(C3H2)8 crystallizes in the tetragonal I4_1/acd space group. The structure consists of thirty-two 2,3-dimethyl-1,3-butadiene molecules and eight WCu4C16H16(N2S)4 clusters inside a WCu4C28S4(NI)4 framework. In each WCu4C16H16(N2S)4 cluster, W(1) is bonded to two equivalent Cu(1), two equivalent Cu(2), and four equivalent S(1) atoms to form distorted WCu4S4 tetrahedra that share edges with two equivalent Cu(1)WS2N2 tetrahedra and edges with two equivalent Cu(2)WS2N2 tetrahedra. Both W(1)-Cu(1) bond lengths are 2.69 Å. Both W(1)-Cu(2) bond lengths are 2.69 Å. All W(1)-S(1) bond lengths are 2.23 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one W(1), two equivalent N(1), and two equivalent S(1) atoms to form distorted CuWS2N2 tetrahedra that share  a cornercorner with one Cu(1)WS2N2 tetrahedra,  an edgeedge with one W(1)Cu4S4 tetrahedra, and edges with two equivalent Cu(2)WS2N2 tetrahedra. Both Cu(1)-N(1) bond lengths are 2.05 Å. Both Cu(1)-S(1) bond lengths are 2.29 Å. In the second Cu site, Cu(2) is bonded to one W(1), two equivalent N(2), and two equivalent S(1) atoms to form distorted CuWS2N2 tetrahedra that share  a cornercorner with one Cu(2)WS2N2 tetrahedra,  an edgeedge with one W(1)Cu4S4 tetrahedra, and edges with two equivalent Cu(1)WS2N2 tetrahedra. Both Cu(2)-N(2) bond lengths are 2.06 Å. Both Cu(2)-S(1) bond lengths are 2.29 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one N(1) and one H(1) atom. The C(1)-N(1) bond length is 1.33 Å. The C(1)-H(1) bond length is 0.95 Å. In the second C site, C(5) is bonded in a distorted bent 120 degrees geometry to one N(1) and one H(4) atom. The C(5)-N(1) bond length is 1.31 Å. The C(5)-H(4) bond length is 0.95 Å. In the third C site, C(6) is bonded in a distorted bent 120 degrees geometry to one N(2) and one H(5) atom. The C(6)-N(2) bond length is 1.34 Å. The C(6)-H(5) bond length is 0.95 Å. In the fourth C site, C(10) is bonded in a distorted bent 120 degrees geometry to one N(2) and one H(8) atom. The C(10)-N(2) bond length is 1.29 Å. The C(10)-H(8) bond length is 0.95 Å. There are two inequivalent N sites. In the first N site, N(2) is bonded in a trigonal planar geometry to one Cu(2), one C(10), and one C(6) atom. In the second N site, N(1) is bonded in a trigonal planar geometry to one Cu(1), one C(1), and one C(5) 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(4) is bonded in a single-bond geometry to one C(5) atom. In the third H site, H(5) is bonded in a single-bond geometry to one C(6) atom. In the fourth H site, H(8) is bonded in a single-bond geometry to one C(10) atom. S(1) is bonded in a distorted trigonal non-coplanar geometry to one W(1), one Cu(1), and one Cu(2) atom. In each WCu4C28S4(NI)4 framework, W(2) is bonded to four equivalent Cu(3) and four equivalent S(2) atoms to form distorted WCu4S4 tetrahedra that share corners with four equivalent N(3)CuC3 tetrahedra. All W(2)-Cu(3) bond lengths are 2.70 Å. All W(2)-S(2) bond lengths are 2.23 Å. Cu(3) is bonded in a 4-coordinate geometry to one W(2), one N(3), two equivalent S(2), and one I(1) atom. The Cu(3)-N(3) bond length is 2.09 Å. There is one shorter (2.31 Å) and one longer (2.33 Å) Cu(3)-S(2) bond length. The Cu(3)-I(1) bond length is 2.58 Å. There are seven inequivalent C sites. In the first C site, C(11) is bonded in a distorted bent 120 degrees geometry to one C(12) and one N(3) atom. The C(11)-C(12) bond length is 1.39 Å. The C(11)-N(3) bond length is 1.34 Å. In the second C site, C(12) is bonded in a bent 120 degrees geometry to one C(11) and one C(13) atom. The C(12)-C(13) bond length is 1.36 Å. In the third C site, C(13) is bonded in a 4-coordinate geometry to one C(12), one C(13), one C(14), and one C(16) atom. The C(13)-C(13) bond length is 1.42 Å. The C(13)-C(14) bond length is 1.56 Å. The C(13)-C(16) bond length is 1.45 Å. In the fourth C site, C(14) is bonded in a 3-coordinate geometry to one C(13), one C(15), and one C(16) atom. The C(14)-C(15) bond length is 1.44 Å. The C(14)-C(16) bond length is 1.36 Å. In the fifth C site, C(15) is bonded in a 3-coordinate geometry to one C(14), one C(17), and one N(3) atom. The C(15)-C(17) bond length is 1.07 Å. The C(15)-N(3) bond length is 1.33 Å. In the sixth C site, C(16) is bonded in a 3-coordinate geometry to one C(13), one C(14), and one C(17) atom. The C(16)-C(17) bond length is 1.41 Å. In the seventh C site, C(17) is bonded in a 2-coordinate geometry to one C(15), one C(16), and one N(3) atom. The C(17)-N(3) bond length is 1.32 Å. N(3) is bonded to one Cu(3), one C(11), one C(15), and one C(17) atom to form distorted NCuC3 tetrahedra that share  a cornercorner with one W(2)Cu4S4 tetrahedra. S(2) is bonded in a distorted trigonal non-coplanar geometry to one W(2) and two equivalent Cu(3) atoms. I(1) is bonded in a single-bond geometry to one Cu(3) atom. Linkers: 16 [C]1=[C]C2(C34[C]=[C]N5[C]6[C]5[C]3[C]64)[C]3[C]4[C]([C]32)N14 ,32 c1cc(-c2ccncc2)ccn1. Metal clusters: 8 [Cu]1[S]2[Cu]3[S]4[Cu][S]5[Cu]6[S]1[W]24536 ,2 I[Cu]1[S]2[Cu@]3(I)[S@]4[Cu@@]5(I)[S]6[Cu](I)[S@@]1[W]62453 ,4 I[Cu]1[S]2[Cu@@]3(I)[S@]4[Cu@]5(I)[S]6[Cu](I)[S@@]1[W]62453 ,2 I[Cu]1[S]2[Cu@]3(I)[S]4[Cu](I)[S]5[Cu@]6(I)[S]1[W]52463. The MOF has largest included sphere 5.20 A, density 2.02 g/cm3, surface area 3164.39 m2/g, accessible volume 0.24 cm3/g