Cu31C48H72S24(N24I)4 crystallizes in the cubic F-43c space group. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 4-coordinate geometry to one Cu(3), one N(2), one N(5), one S(2), and one I(1) atom. The Cu(1)-Cu(3) bond length is 2.76 Å. The Cu(1)-N(2) bond length is 2.00 Å. The Cu(1)-N(5) bond length is 2.00 Å. The Cu(1)-S(2) bond length is 2.32 Å. The Cu(1)-I(1) bond length is 2.79 Å. In the second Cu site, Cu(2) is bonded in a 3-coordinate geometry to one N(1), one N(6), and two equivalent S(1) atoms. The Cu(2)-N(1) bond length is 1.99 Å. The Cu(2)-N(6) bond length is 1.98 Å. There is one shorter (2.26 Å) and one longer (2.99 Å) Cu(2)-S(1) bond length. In the third Cu site, Cu(3) is bonded in a 7-coordinate geometry to three equivalent Cu(1), three equivalent S(2), and one I(1) atom. All Cu(3)-S(2) bond lengths are 2.29 Å. The Cu(3)-I(1) bond length is 3.13 Å. In the fourth Cu site, Cu(4) is bonded in a tetrahedral geometry to four equivalent S(1) atoms. All Cu(4)-S(1) bond lengths are 2.40 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal planar geometry to one N(1), one N(3), and one S(1) atom. The C(1)-N(1) bond length is 1.30 Å. The C(1)-N(3) bond length is 1.36 Å. The C(1)-S(1) bond length is 1.74 Å. In the second C site, C(3) is bonded in a distorted trigonal planar geometry to one N(5), one N(7), and one S(2) atom. The C(3)-N(5) bond length is 1.32 Å. The C(3)-N(7) bond length is 1.35 Å. The C(3)-S(2) bond length is 1.73 Å. In the third C site, C(4) is bonded in a trigonal planar geometry to one N(6), one N(7), and one N(8) atom. The C(4)-N(6) bond length is 1.31 Å. The C(4)-N(7) bond length is 1.35 Å. The C(4)-N(8) bond length is 1.35 Å. In the fourth C site, C(2) is bonded in a trigonal planar geometry to one N(2), one N(3), and one N(4) atom. The C(2)-N(2) bond length is 1.29 Å. The C(2)-N(3) bond length is 1.37 Å. The C(2)-N(4) bond length is 1.38 Å. There are eight inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Cu(2), one C(1), and one N(2) atom. The N(1)-N(2) bond length is 1.41 Å. In the second N site, N(2) is bonded in a 3-coordinate geometry to one Cu(1), one C(2), and one N(1) atom. In the third N site, N(3) is bonded in a distorted trigonal planar geometry to one C(1), one C(2), and one H(1) atom. The N(3)-H(1) bond length is 0.86 Å. In the fourth N site, N(4) is bonded in a trigonal planar geometry to one C(2), one H(2), and one H(3) atom. The N(4)-H(2) bond length is 0.86 Å. The N(4)-H(3) bond length is 0.86 Å. In the fifth N site, N(5) is bonded in a distorted trigonal planar geometry to one Cu(1), one C(3), and one N(6) atom. The N(5)-N(6) bond length is 1.40 Å. In the sixth N site, N(6) is bonded in a 3-coordinate geometry to one Cu(2), one C(4), and one N(5) atom. In the seventh N site, N(7) is bonded in a trigonal planar geometry to one C(3), one C(4), and one H(4) atom. The N(7)-H(4) bond length is 0.86 Å. In the eighth N site, N(8) is bonded in a trigonal planar geometry to one C(4) and two equivalent H(5,6) atoms. Both N(8)-H(5,6) bond lengths are 0.86 Å. There are five inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one N(3) atom. In the second H site, H(2) is bonded in a single-bond geometry to one N(4) atom. In the third H site, H(3) is bonded in a single-bond geometry to one N(4) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one N(7) atom. In the fifth H site, H(5,6) is bonded in a single-bond geometry to one N(8) atom. There are two inequivalent S sites. In the first S site, S(2) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(3), and one C(3) atom. In the second S site, S(1) is bonded in a 4-coordinate geometry to one Cu(4), two equivalent Cu(2), and one C(1) atom. I(1) is bonded in a 4-coordinate geometry to one Cu(3) and three equivalent Cu(1) atoms. Linkers: 192 NC1=N[N]C(=S)N1. Metal clusters: 248 [Cu]. The MOF has largest included sphere 9.74 A, density 1.42 g/cm3, surface area 2989.58 m2/g, accessible volume 0.44 cm3/g