WCu4C36N12H24S4I crystallizes in the orthorhombic Pbca space group. The structure consists of a WCu4C36N12H24S4I framework. W(1) is bonded in a 8-coordinate geometry to one Cu(1), one Cu(2), one Cu(3), one Cu(4), one S(1), one S(2), one S(3), and one S(4) atom. The W(1)-Cu(1) bond length is 2.72 Å. The W(1)-Cu(2) bond length is 2.68 Å. The W(1)-Cu(3) bond length is 2.70 Å. The W(1)-Cu(4) bond length is 2.63 Å. The W(1)-S(1) bond length is 2.18 Å. The W(1)-S(2) bond length is 2.20 Å. The W(1)-S(3) bond length is 2.28 Å. The W(1)-S(4) bond length is 2.18 Å. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one W(1), one N(10), one N(4), one S(1), and one S(3) atom to form distorted CuWS2N2 tetrahedra that share  a cornercorner with one S(3)Cu3W tetrahedra,  an edgeedge with one Cu(2)WS2N2 tetrahedra, and  an edgeedge with one Cu(3)WS2N2 tetrahedra. The Cu(1)-N(10) bond length is 2.00 Å. The Cu(1)-N(4) bond length is 1.98 Å. The Cu(1)-S(1) bond length is 2.29 Å. The Cu(1)-S(3) bond length is 2.32 Å. In the second Cu site, Cu(2) is bonded to one W(1), one N(12), one N(5), one S(3), and one S(4) atom to form distorted CuWS2N2 tetrahedra that share  a cornercorner with one S(3)Cu3W tetrahedra,  an edgeedge with one Cu(1)WS2N2 tetrahedra, and  an edgeedge with one Cu(3)WS2N2 tetrahedra. The Cu(2)-N(12) bond length is 2.11 Å. The Cu(2)-N(5) bond length is 1.97 Å. The Cu(2)-S(3) bond length is 2.28 Å. The Cu(2)-S(4) bond length is 2.26 Å. In the third Cu site, Cu(3) is bonded to one W(1), one N(11), one N(6), one S(2), and one S(3) atom to form distorted CuWS2N2 tetrahedra that share  a cornercorner with one S(3)Cu3W tetrahedra,  an edgeedge with one Cu(1)WS2N2 tetrahedra, and  an edgeedge with one Cu(2)WS2N2 tetrahedra. The Cu(3)-N(11) bond length is 2.06 Å. The Cu(3)-N(6) bond length is 2.02 Å. The Cu(3)-S(2) bond length is 2.28 Å. The Cu(3)-S(3) bond length is 2.30 Å. In the fourth Cu site, Cu(4) is bonded in a 3-coordinate geometry to one W(1), one S(1), one S(2), and one I(1) atom. The Cu(4)-S(1) bond length is 2.24 Å. The Cu(4)-S(2) bond length is 2.30 Å. The Cu(4)-I(1) bond length is 2.35 Å. There are thirty-six inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(4), one N(1), and one N(3) atom. The C(1)-C(4) bond length is 1.51 Å. The C(1)-N(1) bond length is 1.28 Å. The C(1)-N(3) bond length is 1.38 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one C(9), one N(1), and one N(2) atom. The C(2)-C(9) bond length is 1.48 Å. The C(2)-N(1) bond length is 1.32 Å. The C(2)-N(2) bond length is 1.41 Å. In the third C site, C(3) is bonded in a distorted bent 120 degrees geometry to one C(14), one N(2), and one N(3) atom. The C(3)-C(14) bond length is 1.44 Å. The C(3)-N(2) bond length is 1.30 Å. The C(3)-N(3) bond length is 1.30 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(1), one C(5), and one C(8) atom. The C(4)-C(5) bond length is 1.36 Å. The C(4)-C(8) bond length is 1.42 Å. In the fifth C site, C(5) is bonded in a distorted single-bond geometry to one C(4), one C(6), and one H(1) atom. The C(5)-C(6) bond length is 1.36 Å. The C(5)-H(1) bond length is 0.93 Å. In the sixth C site, C(6) is bonded in a 3-coordinate geometry to one C(5), one N(4), and one H(2) atom. The C(6)-N(4) bond length is 1.35 Å. The C(6)-H(2) bond length is 0.93 Å. In the seventh C site, C(7) is bonded in a distorted bent 120 degrees geometry to one N(4) and one H(3) atom. The C(7)-N(4) bond length is 1.36 Å. The C(7)-H(3) bond length is 0.93 Å. In the eighth C site, C(8) is bonded in a distorted single-bond geometry to one C(4) and one H(4) atom. The C(8)-H(4) bond length is 0.93 Å. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one C(10), one C(13), and one C(2) atom. The C(9)-C(10) bond length is 1.45 Å. The C(9)-C(13) bond length is 1.35 Å. In the tenth C site, C(10) is bonded in a distorted single-bond geometry to one C(9) and one H(5) atom. The C(10)-H(5) bond length is 0.93 Å. In the eleventh C site, C(11) is bonded in a distorted bent 120 degrees geometry to one N(5) and one H(6) atom. The C(11)-N(5) bond length is 1.42 Å. The C(11)-H(6) bond length is 0.93 Å. In the twelfth C site, C(12) is bonded in a distorted bent 120 degrees geometry to one N(5) and one H(7) atom. The C(12)-N(5) bond length is 1.39 Å. The C(12)-H(7) bond length is 0.93 Å. In the thirteenth C site, C(13) is bonded in a distorted single-bond geometry to one C(9) and one H(8) atom. The C(13)-H(8) bond length is 0.93 Å. In the fourteenth C site, C(14) is bonded in a trigonal planar geometry to one C(15), one C(18), and one C(3) atom. The C(14)-C(15) bond length is 1.36 Å. The C(14)-C(18) bond length is 1.43 Å. In the fifteenth C site, C(15) is bonded in a distorted single-bond geometry to one C(14) and one H(9) atom. The C(15)-H(9) bond length is 0.93 Å. In the sixteenth C site, C(16) is bonded in a distorted bent 120 degrees geometry to one N(6) and one H(10) atom. The C(16)-N(6) bond length is 1.42 Å. The C(16)-H(10) bond length is 0.93 Å. In the seventeenth C site, C(17) is bonded in a distorted bent 120 degrees geometry to one N(6) and one H(11) atom. The C(17)-N(6) bond length is 1.24 Å. The C(17)-H(11) bond length is 0.93 Å. In the eighteenth C site, C(18) is bonded in a distorted single-bond geometry to one C(14) and one H(12) atom. The C(18)-H(12) bond length is 0.93 Å. In the nineteenth C site, C(19) is bonded in a distorted bent 120 degrees geometry to one C(22), one N(7), and one N(9) atom. The C(19)-C(22) bond length is 1.50 Å. The C(19)-N(7) bond length is 1.30 Å. The C(19)-N(9) bond length is 1.40 Å. In the twentieth C site, C(20) is bonded in a distorted trigonal planar geometry to one C(27), one N(7), and one N(8) atom. The C(20)-C(27) bond length is 1.44 Å. The C(20)-N(7) bond length is 1.38 Å. The C(20)-N(8) bond length is 1.33 Å. In the twenty-first C site, C(21) is bonded in a 2-coordinate geometry to one C(32), one N(8), and one N(9) atom. The C(21)-C(32) bond length is 1.51 Å. The C(21)-N(8) bond length is 1.34 Å. The C(21)-N(9) bond length is 1.26 Å. In the twenty-second C site, C(22) is bonded in a trigonal planar geometry to one C(19), one C(23), and one C(26) atom. The C(22)-C(23) bond length is 1.42 Å. The C(22)-C(26) bond length is 1.40 Å. In the twenty-third C site, C(23) is bonded in a distorted single-bond geometry to one C(22), one C(24), and one H(13) atom. The C(23)-C(24) bond length is 1.32 Å. The C(23)-H(13) bond length is 0.93 Å. In the twenty-fourth C site, C(24) is bonded in a distorted trigonal planar geometry to one C(23), one N(10), and one H(14) atom. The C(24)-N(10) bond length is 1.37 Å. The C(24)-H(14) bond length is 0.93 Å. In the twenty-fifth C site, C(25) is bonded in a distorted bent 120 degrees geometry to one C(26), one N(10), and one H(15) atom. The C(25)-C(26) bond length is 1.40 Å. The C(25)-N(10) bond length is 1.37 Å. The C(25)-H(15) bond length is 0.93 Å. In the twenty-sixth C site, C(26) is bonded in a distorted single-bond geometry to one C(22), one C(25), and one H(16) atom. The C(26)-H(16) bond length is 0.93 Å. In the twenty-seventh C site, C(27) is bonded in a trigonal planar geometry to one C(20), one C(28), and one C(31) atom. The C(27)-C(28) bond length is 1.47 Å. The C(27)-C(31) bond length is 1.42 Å. In the twenty-eighth C site, C(28) is bonded in a distorted single-bond geometry to one C(27), one C(29), and one H(17) atom. The C(28)-C(29) bond length is 1.30 Å. The C(28)-H(17) bond length is 0.93 Å. In the twenty-ninth C site, C(29) is bonded in a distorted trigonal planar geometry to one C(28), one N(11), and one H(18) atom. The C(29)-N(11) bond length is 1.40 Å. The C(29)-H(18) bond length is 0.93 Å. In the thirtieth C site, C(30) is bonded in a distorted trigonal planar geometry to one C(31), one N(11), and one H(19) atom. The C(30)-C(31) bond length is 1.35 Å. The C(30)-N(11) bond length is 1.42 Å. The C(30)-H(19) bond length is 0.93 Å. In the thirty-first C site, C(31) is bonded in a distorted single-bond geometry to one C(27), one C(30), and one H(20) atom. The C(31)-H(20) bond length is 0.93 Å. In the thirty-second C site, C(32) is bonded in a trigonal planar geometry to one C(21), one C(33), and one C(36) atom. The C(32)-C(33) bond length is 1.47 Å. The C(32)-C(36) bond length is 1.32 Å. In the thirty-third C site, C(33) is bonded in a distorted single-bond geometry to one C(32), one C(34), and one H(21) atom. The C(33)-C(34) bond length is 1.26 Å. The C(33)-H(21) bond length is 0.93 Å. In the thirty-fourth C site, C(34) is bonded in a distorted trigonal planar geometry to one C(33), one N(12), and one H(22) atom. The C(34)-N(12) bond length is 1.33 Å. The C(34)-H(22) bond length is 0.93 Å. In the thirty-fifth C site, C(35) is bonded in a distorted bent 120 degrees geometry to one N(12) and one H(23) atom. The C(35)-N(12) bond length is 1.32 Å. The C(35)-H(23) bond length is 0.93 Å. In the thirty-sixth C site, C(36) is bonded in a distorted single-bond geometry to one C(32) and one H(24) atom. The C(36)-H(24) bond length is 0.93 Å. There are twelve inequivalent N sites. In the first N site, N(1) is bonded in a bent 120 degrees geometry to one C(1) and one C(2) atom. In the second N site, N(2) is bonded in a bent 120 degrees geometry to one C(2) and one C(3) atom. In the third N site, N(3) is bonded in a bent 120 degrees geometry to one C(1) and one C(3) atom. In the fourth N site, N(4) is bonded in a trigonal planar geometry to one Cu(1), one C(6), and one C(7) atom. In the fifth N site, N(5) is bonded in a trigonal planar geometry to one Cu(2), one C(11), and one C(12) atom. In the sixth N site, N(6) is bonded in a trigonal planar geometry to one Cu(3), one C(16), and one C(17) atom. In the seventh N site, N(7) is bonded in a bent 120 degrees geometry to one C(19) and one C(20) atom. In the eighth N site, N(8) is bonded in a bent 120 degrees geometry to one C(20) and one C(21) atom. In the ninth N site, N(9) is bonded in a bent 120 degrees geometry to one C(19) and one C(21) atom. In the tenth N site, N(10) is bonded in a trigonal planar geometry to one Cu(1), one C(24), and one C(25) atom. In the eleventh N site, N(11) is bonded in a trigonal planar geometry to one Cu(3), one C(29), and one C(30) atom. In the twelfth N site, N(12) is bonded in a trigonal planar geometry to one Cu(2), one C(34), and one C(35) atom. There are twenty-four 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(2) is bonded in a single-bond geometry to one C(6) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(7) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(8) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(10) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(11) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(12) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(13) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(15) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one C(16) atom. In the eleventh H site, H(11) is bonded in a single-bond geometry to one C(17) atom. In the twelfth H site, H(12) is bonded in a single-bond geometry to one C(18) atom. In the thirteenth H site, H(13) is bonded in a single-bond geometry to one C(23) atom. In the fourteenth H site, H(14) is bonded in a single-bond geometry to one C(24) atom. In the fifteenth H site, H(15) is bonded in a single-bond geometry to one C(25) atom. In the sixteenth H site, H(16) is bonded in a single-bond geometry to one C(26) atom. In the seventeenth H site, H(17) is bonded in a single-bond geometry to one C(28) atom. In the eighteenth H site, H(18) is bonded in a single-bond geometry to one C(29) atom. In the nineteenth H site, H(19) is bonded in a single-bond geometry to one C(30) atom. In the twentieth H site, H(20) is bonded in a single-bond geometry to one C(31) atom. In the twenty-first H site, H(21) is bonded in a single-bond geometry to one C(33) atom. In the twenty-second H site, H(22) is bonded in a single-bond geometry to one C(34) atom. In the twenty-third H site, H(23) is bonded in a single-bond geometry to one C(35) atom. In the twenty-fourth H site, H(24) is bonded in a single-bond geometry to one C(36) atom. There are four inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal non-coplanar geometry to one W(1), one Cu(1), and one Cu(4) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to one W(1), one Cu(3), and one Cu(4) atom. In the third S site, S(3) is bonded to one W(1), one Cu(1), one Cu(2), and one Cu(3) atom to form distorted SCu3W tetrahedra that share  a cornercorner with one Cu(1)WS2N2 tetrahedra,  a cornercorner with one Cu(2)WS2N2 tetrahedra, and  a cornercorner with one Cu(3)WS2N2 tetrahedra. In the fourth S site, S(4) is bonded in a 2-coordinate geometry to one W(1) and one Cu(2) atom. I(1) is bonded in a single-bond geometry to one Cu(4) atom. Linkers: 16 n1ccc(cc1)C1=NC(=[N]=C([N]1)c1ccncc1)c1ccncc1. Metal clusters: 2 I[Cu@]12[S]3[Cu][S@@]45[Cu][S]1[W]3421S[Cu]51 ,24 [Cu] ,6 [W]. The MOF has largest included sphere 6.86 A, density 1.60 g/cm3, surface area 3338.24 m2/g, accessible volume 0.28 cm3/g