Zn5C46H34S2(N2O3)6 crystallizes in the triclinic P-1 space group. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one N(2), one O(4), one O(6), and one O(7) atom to form corner-sharing ZnNO3 tetrahedra. The corner-sharing octahedral tilt angles are 63°. The Zn(1)-N(2) bond length is 2.03 Å. The Zn(1)-O(4) bond length is 2.02 Å. The Zn(1)-O(6) bond length is 1.90 Å. The Zn(1)-O(7) bond length is 1.92 Å. In the second Zn site, Zn(2) is bonded in a distorted rectangular see-saw-like geometry to one N(3), one O(7), one O(8), and one O(9) atom. The Zn(2)-N(3) bond length is 2.02 Å. The Zn(2)-O(7) bond length is 1.92 Å. The Zn(2)-O(8) bond length is 1.95 Å. The Zn(2)-O(9) bond length is 2.45 Å. In the third Zn site, Zn(3) is bonded to two equivalent N(1), two equivalent O(5), and two equivalent O(6) atoms to form corner-sharing ZnN2O4 octahedra. Both Zn(3)-N(1) bond lengths are 2.21 Å. Both Zn(3)-O(5) bond lengths are 2.22 Å. Both Zn(3)-O(6) bond lengths are 1.94 Å. There are twenty-three inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(4), one O(4), and one O(5) atom. The C(1)-C(4) bond length is 1.53 Å. The C(1)-O(4) bond length is 1.25 Å. The C(1)-O(5) bond length is 1.26 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one C(21) and one H(3) atom. The C(2)-C(21) bond length is 1.35 Å. The C(2)-H(3) bond length is 0.93 Å. In the third C site, C(3) is bonded in a distorted bent 120 degrees geometry to one N(1) and one H(4) atom. The C(3)-N(1) bond length is 1.32 Å. The C(3)-H(4) bond length is 0.93 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(1), one C(7), and one C(8) atom. The C(4)-C(7) bond length is 1.41 Å. The C(4)-C(8) bond length is 1.36 Å. In the fifth C site, C(5) is bonded in a distorted trigonal planar geometry to one C(13), one N(1), and one H(5) atom. The C(5)-C(13) bond length is 1.36 Å. The C(5)-N(1) bond length is 1.33 Å. The C(5)-H(5) bond length is 0.93 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to one C(17) and one H(6) atom. The C(6)-C(17) bond length is 1.39 Å. The C(6)-H(6) bond length is 0.93 Å. In the seventh C site, C(7) is bonded in a distorted single-bond geometry to one C(11), one C(4), and one H(7) atom. The C(7)-C(11) bond length is 1.39 Å. The C(7)-H(7) 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), one C(9), and one H(8) atom. The C(8)-C(9) bond length is 1.41 Å. The C(8)-H(8) bond length is 0.93 Å. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one C(15), one C(18), and one C(8) atom. The C(9)-C(15) bond length is 1.46 Å. The C(9)-C(18) bond length is 1.41 Å. In the tenth C site, C(10) is bonded in a distorted bent 120 degrees geometry to one C(22), one N(2), and one H(9) atom. The C(10)-C(22) bond length is 1.35 Å. The C(10)-N(2) bond length is 1.33 Å. The C(10)-H(9) bond length is 0.93 Å. In the eleventh C site, C(11) is bonded in a trigonal planar geometry to one C(18), one C(7), and one S(1) atom. The C(11)-C(18) bond length is 1.33 Å. The C(11)-S(1) bond length is 1.85 Å. In the twelfth C site, C(12) is bonded in a distorted trigonal planar geometry to one C(14), one C(16), and one N(6) atom. The C(12)-C(14) bond length is 1.37 Å. The C(12)-C(16) bond length is 1.37 Å. The C(12)-N(6) bond length is 1.38 Å. In the thirteenth C site, C(13) is bonded in a distorted single-bond geometry to one C(21), one C(5), and one H(10) atom. The C(13)-C(21) bond length is 1.37 Å. The C(13)-H(10) bond length is 0.93 Å. In the fourteenth C site, C(14) is bonded in a distorted single-bond geometry to one C(12), one C(19), and one H(11) atom. The C(14)-C(19) bond length is 1.32 Å. The C(14)-H(11) bond length is 0.93 Å. In the fifteenth C site, C(15) is bonded in a bent 120 degrees geometry to one C(9), one O(8), and one O(9) atom. The C(15)-O(8) bond length is 1.28 Å. The C(15)-O(9) bond length is 1.23 Å. In the sixteenth C site, C(16) is bonded in a distorted single-bond geometry to one C(12) and one H(12) atom. The C(16)-H(12) bond length is 0.93 Å. In the seventeenth C site, C(17) is bonded in a distorted trigonal planar geometry to one C(22), one C(6), and one N(4) atom. The C(17)-C(22) bond length is 1.34 Å. The C(17)-N(4) bond length is 1.45 Å. In the eighteenth C site, C(18) is bonded in a distorted single-bond geometry to one C(11), one C(9), and one H(13) atom. The C(18)-H(13) bond length is 0.93 Å. In the nineteenth C site, C(19) is bonded in a distorted trigonal planar geometry to one C(14), one N(3), and one H(14) atom. The C(19)-N(3) bond length is 1.34 Å. The C(19)-H(14) bond length is 0.93 Å. In the twentieth C site, C(20) is bonded in a distorted bent 120 degrees geometry to one N(2) and one H(15) atom. The C(20)-N(2) bond length is 1.31 Å. The C(20)-H(15) bond length is 0.93 Å. In the twenty-first C site, C(21) is bonded in a distorted trigonal planar geometry to one C(13), one C(2), and one N(5) atom. The C(21)-N(5) bond length is 1.45 Å. In the twenty-second C site, C(22) is bonded in a distorted single-bond geometry to one C(10), one C(17), and one H(16) atom. The C(22)-H(16) bond length is 0.93 Å. In the twenty-third C site, C(23) is bonded in a distorted bent 120 degrees geometry to one N(3) and one H(17) atom. The C(23)-N(3) bond length is 1.33 Å. The C(23)-H(17) bond length is 0.93 Å. There are six inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Zn(3), one C(3), and one C(5) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Zn(1), one C(10), and one C(20) atom. In the third N site, N(3) is bonded in a trigonal planar geometry to one Zn(2), one C(19), and one C(23) atom. In the fourth N site, N(4) is bonded in a distorted water-like geometry to one C(17) and one N(5) atom. The N(4)-N(5) bond length is 1.15 Å. In the fifth N site, N(5) is bonded in a distorted water-like geometry to one C(21) and one N(4) atom. In the sixth N site, N(6) is bonded in a distorted bent 120 degrees geometry to one C(12) and one N(6) atom. The N(6)-N(6) bond length is 1.23 Å. There are seventeen inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(6) atom. The H(1)-O(6) bond length is 0.85 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(7) atom. The H(2)-O(7) bond length is 0.85 Å. In the third H site, H(3) is bonded in a single-bond geometry to one C(2) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(3) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(5) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(6) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(7) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(8) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(10) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one C(13) atom. In the eleventh H site, H(11) is bonded in a single-bond geometry to one C(14) atom. In the twelfth H site, H(12) is bonded in a single-bond geometry to one C(16) atom. In the thirteenth H site, H(13) is bonded in a single-bond geometry to one C(18) atom. In the fourteenth H site, H(14) is bonded in a single-bond geometry to one C(19) atom. In the fifteenth H site, H(15) is bonded in a single-bond geometry to one C(20) atom. In the sixteenth H site, H(16) is bonded in a single-bond geometry to one C(22) atom. In the seventeenth H site, H(17) is bonded in a single-bond geometry to one C(23) atom. S(1) is bonded in a distorted trigonal non-coplanar geometry to one C(11), one O(1), one O(2), and one O(3) atom. The S(1)-O(1) bond length is 1.38 Å. The S(1)-O(2) bond length is 1.36 Å. The S(1)-O(3) bond length is 1.40 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one S(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one S(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to one S(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Zn(1) and one C(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Zn(3) and one C(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Zn(1), one Zn(3), and one H(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(2), and one H(2) atom. In the eighth O site, O(8) is bonded in a water-like geometry to one Zn(2) and one C(15) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Zn(2) and one C(15) atom. Linkers: 2 [O]C(=O)c1cc(C([O])=O)cc(S([O])([O])[O])c1 ,3 c1cc([N][N]c2ccncc2)ccn1. Metal clusters: 1 O=[C]O[Zn]O.O=[C]O[Zn]O.O[Zn]O[C]O[Zn]O[C]O[Zn]O. The MOF has largest included sphere 5.06 A, density 1.48 g/cm3, surface area 4196.20 m2/g, accessible volume 0.30 cm3/g