Na2Zn5C40H20S4(N3O7)4 crystallizes in the triclinic P-1 space group. Na(1) is bonded to one O(10), one O(13), one O(4), one O(6), and one O(7) atom to form distorted NaO5 square pyramids that share  an edgeedge with one Zn(1)N2O2 tetrahedra. The Na(1)-O(10) bond length is 2.37 Å. The Na(1)-O(13) bond length is 2.35 Å. The Na(1)-O(4) bond length is 2.43 Å. The Na(1)-O(6) bond length is 2.53 Å. The Na(1)-O(7) bond length is 2.45 Å. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one N(1), one N(4), one O(10), and one O(4) atom to form ZnN2O2 tetrahedra that share  an edgeedge with one Na(1)O5 square pyramid. The Zn(1)-N(1) bond length is 1.99 Å. The Zn(1)-N(4) bond length is 2.01 Å. The Zn(1)-O(10) bond length is 1.98 Å. The Zn(1)-O(4) bond length is 2.00 Å. In the second Zn site, Zn(2) is bonded in a tetrahedral geometry to one N(3), one N(5), one O(2), and one O(9) atom. The Zn(2)-N(3) bond length is 1.98 Å. The Zn(2)-N(5) bond length is 2.00 Å. The Zn(2)-O(2) bond length is 1.97 Å. The Zn(2)-O(9) bond length is 1.90 Å. In the third Zn site, Zn(3) is bonded in an octahedral geometry to two equivalent N(2), two equivalent N(6), and two equivalent O(1) atoms. Both Zn(3)-N(2) bond lengths are 2.13 Å. Both Zn(3)-N(6) bond lengths are 2.11 Å. Both Zn(3)-O(1) bond lengths are 2.13 Å. There are twenty inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one N(1), one N(2), and one H(1) atom. The C(1)-N(1) bond length is 1.33 Å. The C(1)-N(2) bond length is 1.32 Å. The C(1)-H(1) bond length is 0.95 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one N(1), one N(3), and one H(2) atom. The C(2)-N(1) bond length is 1.35 Å. The C(2)-N(3) bond length is 1.32 Å. The C(2)-H(2) bond length is 0.95 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one N(4), one N(5), and one H(3) atom. The C(3)-N(4) bond length is 1.34 Å. The C(3)-N(5) bond length is 1.33 Å. The C(3)-H(3) bond length is 0.95 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one N(4), one N(6), and one H(4) atom. The C(4)-N(4) bond length is 1.34 Å. The C(4)-N(6) bond length is 1.32 Å. The C(4)-H(4) bond length is 0.95 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one C(10), one C(6), and one S(1) atom. The C(5)-C(10) bond length is 1.39 Å. The C(5)-C(6) bond length is 1.39 Å. The C(5)-S(1) bond length is 1.76 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to one C(5), one C(7), and one H(5) atom. The C(6)-C(7) bond length is 1.39 Å. The C(6)-H(5) bond length is 0.95 Å. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one C(11), one C(6), and one C(8) atom. The C(7)-C(11) bond length is 1.51 Å. The C(7)-C(8) bond length is 1.39 Å. In the eighth C site, C(8) is bonded in a distorted single-bond geometry to one C(7), one C(9), and one H(6) atom. The C(8)-C(9) bond length is 1.41 Å. The C(8)-H(6) bond length is 0.95 Å. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one C(10), one C(12), and one C(8) atom. The C(9)-C(10) bond length is 1.38 Å. The C(9)-C(12) bond length is 1.49 Å. In the tenth C site, C(10) is bonded in a distorted single-bond geometry to one C(5), one C(9), and one H(7) atom. The C(10)-H(7) bond length is 0.95 Å. In the eleventh C site, C(11) is bonded in a distorted bent 120 degrees geometry to one C(7), one O(1), and one O(2) atom. The C(11)-O(1) bond length is 1.24 Å. The C(11)-O(2) bond length is 1.26 Å. In the twelfth C site, C(12) is bonded in a distorted bent 120 degrees geometry to one C(9), one O(3), and one O(4) atom. The C(12)-O(3) bond length is 1.25 Å. The C(12)-O(4) bond length is 1.28 Å. In the thirteenth C site, C(13) is bonded in a trigonal planar geometry to one C(14), one C(18), and one S(2) atom. The C(13)-C(14) bond length is 1.38 Å. The C(13)-C(18) bond length is 1.37 Å. The C(13)-S(2) bond length is 1.78 Å. In the fourteenth C site, C(14) is bonded in a distorted single-bond geometry to one C(13), one C(15), and one H(8) atom. The C(14)-C(15) bond length is 1.40 Å. The C(14)-H(8) bond length is 0.95 Å. In the fifteenth C site, C(15) is bonded in a trigonal planar geometry to one C(14), one C(16), and one C(19) atom. The C(15)-C(16) bond length is 1.39 Å. The C(15)-C(19) bond length is 1.50 Å. In the sixteenth C site, C(16) is bonded in a distorted single-bond geometry to one C(15), one C(17), and one H(9) atom. The C(16)-C(17) bond length is 1.38 Å. The C(16)-H(9) bond length is 0.95 Å. In the seventeenth C site, C(17) is bonded in a trigonal planar geometry to one C(16), one C(18), and one C(20) atom. The C(17)-C(18) bond length is 1.40 Å. The C(17)-C(20) bond length is 1.49 Å. In the eighteenth C site, C(18) is bonded in a distorted single-bond geometry to one C(13), one C(17), and one H(10) atom. The C(18)-H(10) bond length is 0.95 Å. In the nineteenth C site, C(19) is bonded in a distorted bent 120 degrees geometry to one C(15), one O(8), and one O(9) atom. The C(19)-O(8) bond length is 1.22 Å. The C(19)-O(9) bond length is 1.25 Å. In the twentieth C site, C(20) is bonded in a distorted bent 120 degrees geometry to one C(17), one O(10), and one O(11) atom. The C(20)-O(10) bond length is 1.27 Å. The C(20)-O(11) bond length is 1.25 Å. There are six inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Zn(1), one C(1), and one C(2) atom. In the second N site, N(2) is bonded in a 3-coordinate geometry to one Zn(3), one C(1), and one N(3) atom. The N(2)-N(3) bond length is 1.36 Å. In the third N site, N(3) is bonded in a distorted trigonal planar geometry to one Zn(2), one C(2), and one N(2) atom. In the fourth N site, N(4) is bonded in a trigonal planar geometry to one Zn(1), one C(3), and one C(4) atom. In the fifth N site, N(5) is bonded in a distorted trigonal planar geometry to one Zn(2), one C(3), and one N(6) atom. The N(5)-N(6) bond length is 1.36 Å. In the sixth N site, N(6) is bonded in a 3-coordinate geometry to one Zn(3), one C(4), and one N(5) atom. There are ten 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(2) is bonded in a single-bond geometry to one C(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(3) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(4) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(6) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(8) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(10) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(14) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(16) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one C(18) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal non-coplanar geometry to one C(5), one O(5), one O(6), and one O(7) atom. The S(1)-O(5) bond length is 1.47 Å. The S(1)-O(6) bond length is 1.46 Å. The S(1)-O(7) bond length is 1.45 Å. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one C(13), one O(12), one O(13), and one O(14) atom. The S(2)-O(12) bond length is 1.44 Å. The S(2)-O(13) bond length is 1.43 Å. The S(2)-O(14) bond length is 1.46 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Zn(3) and one C(11) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Zn(2) and one C(11) atom. In the third O site, O(3) is bonded in a single-bond geometry to one C(12) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one C(12) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one S(1) atom. In the sixth O site, O(6) is bonded in a distorted L-shaped geometry to one Na(1) and one S(1) atom. In the seventh O site, O(7) is bonded in a distorted L-shaped geometry to one Na(1) and one S(1) atom. In the eighth O site, O(8) is bonded in a single-bond geometry to one C(19) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one Zn(2) and one C(19) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one C(20) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one C(20) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one S(2) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Na(1) and one S(2) atom. In the fourteenth O site, O(14) is bonded in a single-bond geometry to one S(2) atom. Linkers: 2 [O]C(=O)c1cc(C([O])=O)cc(S([O])([O])[O])c1 ,2 [N]1=CN=NC=1 ,2 C1=NC=N[N]1 ,2 [O]C(=O)c1cc([S]=O)cc(C([O])=O)c1. Metal clusters: 2 O=S(=O)=O.O=[C]O[Zn]O[C]=O.[O][S@@](=O)O[Na] ,1 O=[C]O[Zn@]12N=N[Zn]34(N=N1)(N=N[Zn@@](O[C]=O)(N=N3)O[C]O4)O[C]O2. The MOF has largest included sphere 4.23 A, density 1.40 g/cm3, surface area 3618.14 m2/g, accessible volume 0.33 cm3/g