Zn4C33NH25O16 crystallizes in the orthorhombic P2_12_12_1 space group. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), one O(10), one O(13), one O(15), one O(16), and one O(4) atom to form corner-sharing ZnO6 octahedra. The Zn(1)-O(1) bond length is 2.07 Å. The Zn(1)-O(10) bond length is 2.17 Å. The Zn(1)-O(13) bond length is 2.17 Å. The Zn(1)-O(15) bond length is 2.14 Å. The Zn(1)-O(16) bond length is 2.10 Å. The Zn(1)-O(4) bond length is 2.10 Å. In the second Zn site, Zn(2) is bonded to one O(1), one O(12), one O(5), and one O(7) atom to form ZnO4 tetrahedra that share  a cornercorner with one Zn(1)O6 octahedra,  a cornercorner with one Zn(3)O4 tetrahedra, and  a cornercorner with one Zn(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 77°. The Zn(2)-O(1) bond length is 1.97 Å. The Zn(2)-O(12) bond length is 1.95 Å. The Zn(2)-O(5) bond length is 1.97 Å. The Zn(2)-O(7) bond length is 2.00 Å. In the third Zn site, Zn(3) is bonded to one O(1), one O(14), one O(3), and one O(6) atom to form ZnO4 tetrahedra that share  a cornercorner with one Zn(1)O6 octahedra,  a cornercorner with one Zn(2)O4 tetrahedra, and  a cornercorner with one Zn(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 69°. The Zn(3)-O(1) bond length is 1.94 Å. The Zn(3)-O(14) bond length is 1.94 Å. The Zn(3)-O(3) bond length is 2.05 Å. The Zn(3)-O(6) bond length is 2.00 Å. In the fourth Zn site, Zn(4) is bonded to one O(1), one O(11), one O(2), and one O(8) atom to form distorted ZnO4 tetrahedra that share  a cornercorner with one Zn(1)O6 octahedra,  a cornercorner with one Zn(2)O4 tetrahedra, and  a cornercorner with one Zn(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 73°. The Zn(4)-O(1) bond length is 1.93 Å. The Zn(4)-O(11) bond length is 1.94 Å. The Zn(4)-O(2) bond length is 2.03 Å. The Zn(4)-O(8) bond length is 2.05 Å. There are thirty-three inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one C(2), one C(6), and one C(7) atom. The C(1)-C(2) bond length is 1.39 Å. The C(1)-C(6) bond length is 1.39 Å. The C(1)-C(7) bond length is 1.50 Å. In the second C site, C(2) is bonded in a distorted trigonal planar geometry to one C(1), one C(3), and one H(1) atom. The C(2)-C(3) bond length is 1.40 Å. The C(2)-H(1) bond length is 1.09 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(2), one C(4), and one C(8) atom. The C(3)-C(4) bond length is 1.40 Å. The C(3)-C(8) bond length is 1.50 Å. In the fourth C site, C(4) is bonded in a distorted trigonal planar geometry to one C(3), one C(5), and one H(2) atom. The C(4)-C(5) bond length is 1.41 Å. The C(4)-H(2) bond length is 1.09 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one C(4), one C(6), and one C(9) atom. The C(5)-C(6) bond length is 1.40 Å. The C(5)-C(9) bond length is 1.48 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to one C(1), one C(5), and one H(3) atom. The C(6)-H(3) bond length is 1.09 Å. In the seventh C site, C(7) is bonded in a distorted bent 120 degrees geometry to one C(1), one O(4), and one O(5) atom. The C(7)-O(4) bond length is 1.26 Å. The C(7)-O(5) bond length is 1.28 Å. In the eighth C site, C(8) is bonded in a distorted bent 120 degrees geometry to one C(3), one O(6), and one O(7) atom. The C(8)-O(6) bond length is 1.28 Å. The C(8)-O(7) bond length is 1.28 Å. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one C(10), one C(14), and one C(5) atom. The C(9)-C(10) bond length is 1.40 Å. The C(9)-C(14) bond length is 1.41 Å. In the tenth C site, C(10) is bonded in a distorted single-bond geometry to one C(9) and one H(4) atom. The C(10)-H(4) bond length is 1.09 Å. In the eleventh C site, C(11) is bonded in a distorted single-bond geometry to one C(12) and one H(5) atom. The C(11)-C(12) bond length is 1.40 Å. The C(11)-H(5) bond length is 1.09 Å. In the twelfth C site, C(12) is bonded in a trigonal planar geometry to one C(11), one C(13), and one C(15) atom. The C(12)-C(13) bond length is 1.40 Å. The C(12)-C(15) bond length is 1.47 Å. In the thirteenth C site, C(13) is bonded in a distorted trigonal planar geometry to one C(12), one C(14), and one H(6) atom. The C(13)-C(14) bond length is 1.39 Å. The C(13)-H(6) bond length is 1.09 Å. In the fourteenth C site, C(14) is bonded in a distorted single-bond geometry to one C(13), one C(9), and one H(7) atom. The C(14)-H(7) bond length is 1.09 Å. In the fifteenth C site, C(15) is bonded in a distorted bent 120 degrees geometry to one C(12), one O(8), and one O(9) atom. The C(15)-O(8) bond length is 1.26 Å. The C(15)-O(9) bond length is 1.31 Å. In the sixteenth C site, C(16) is bonded in a trigonal planar geometry to one C(17), one C(21), and one C(22) atom. The C(16)-C(17) bond length is 1.40 Å. The C(16)-C(21) bond length is 1.40 Å. The C(16)-C(22) bond length is 1.50 Å. In the seventeenth C site, C(17) is bonded in a distorted trigonal planar geometry to one C(16), one C(18), and one H(8) atom. The C(17)-C(18) bond length is 1.40 Å. The C(17)-H(8) bond length is 1.09 Å. In the eighteenth C site, C(18) is bonded in a trigonal planar geometry to one C(17), one C(19), and one C(23) atom. The C(18)-C(19) bond length is 1.40 Å. The C(18)-C(23) bond length is 1.50 Å. In the nineteenth C site, C(19) is bonded in a distorted single-bond geometry to one C(18), one C(20), and one H(9) atom. The C(19)-C(20) bond length is 1.40 Å. The C(19)-H(9) bond length is 1.09 Å. In the twentieth C site, C(20) is bonded in a trigonal planar geometry to one C(19), one C(21), and one C(24) atom. The C(20)-C(21) bond length is 1.40 Å. The C(20)-C(24) bond length is 1.48 Å. In the twenty-first C site, C(21) is bonded in a distorted single-bond geometry to one C(16), one C(20), and one H(10) atom. The C(21)-H(10) bond length is 1.09 Å. In the twenty-second C site, C(22) is bonded in a distorted bent 120 degrees geometry to one C(16), one O(10), and one O(11) atom. The C(22)-O(10) bond length is 1.26 Å. The C(22)-O(11) bond length is 1.29 Å. In the twenty-third C site, C(23) is bonded in a distorted bent 120 degrees geometry to one C(18), one O(12), and one O(13) atom. The C(23)-O(12) bond length is 1.29 Å. The C(23)-O(13) bond length is 1.26 Å. In the twenty-fourth C site, C(24) is bonded in a trigonal planar geometry to one C(20), one C(25), and one C(29) atom. The C(24)-C(25) bond length is 1.41 Å. The C(24)-C(29) bond length is 1.41 Å. In the twenty-fifth C site, C(25) is bonded in a distorted single-bond geometry to one C(24) and one H(11) atom. The C(25)-H(11) bond length is 1.09 Å. In the twenty-sixth C site, C(26) is bonded in a distorted single-bond geometry to one C(27) and one H(12) atom. The C(26)-C(27) bond length is 1.40 Å. The C(26)-H(12) bond length is 1.09 Å. In the twenty-seventh C site, C(27) is bonded in a trigonal planar geometry to one C(26), one C(28), and one C(30) atom. The C(27)-C(28) bond length is 1.40 Å. The C(27)-C(30) bond length is 1.49 Å. In the twenty-eighth C site, C(28) is bonded in a distorted trigonal planar geometry to one C(27), one C(29), and one H(13) atom. The C(28)-C(29) bond length is 1.39 Å. The C(28)-H(13) bond length is 1.09 Å. In the twenty-ninth C site, C(29) is bonded in a distorted trigonal planar geometry to one C(24), one C(28), and one H(14) atom. The C(29)-H(14) bond length is 1.09 Å. In the thirtieth C site, C(30) is bonded in a distorted bent 120 degrees geometry to one C(27), one O(14), and one O(15) atom. The C(30)-O(14) bond length is 1.29 Å. The C(30)-O(15) bond length is 1.26 Å. In the thirty-first C site, C(31) is bonded in a trigonal planar geometry to one N(1), one H(15), and one O(16) atom. The C(31)-N(1) bond length is 1.34 Å. The C(31)-H(15) bond length is 1.10 Å. The C(31)-O(16) bond length is 1.25 Å. In the thirty-second C site, C(32) is bonded to one N(1), one H(16), one H(17), and one H(18) atom to form corner-sharing CH3N tetrahedra. The C(32)-N(1) bond length is 1.45 Å. The C(32)-H(16) bond length is 1.10 Å. The C(32)-H(17) bond length is 1.10 Å. The C(32)-H(18) bond length is 1.10 Å. In the thirty-third C site, C(33) is bonded to one N(1), one H(19), one H(20), and one H(21) atom to form corner-sharing CH3N tetrahedra. The C(33)-N(1) bond length is 1.45 Å. The C(33)-H(19) bond length is 1.10 Å. The C(33)-H(20) bond length is 1.10 Å. The C(33)-H(21) bond length is 1.09 Å. N(1) is bonded in a trigonal planar geometry to one C(31), one C(32), and one C(33) atom. There are twenty-five inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(4) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(6) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(10) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(11) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(13) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(14) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(17) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(19) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one C(21) atom. In the eleventh H site, H(11) is bonded in a single-bond geometry to one C(25) atom. In the twelfth H site, H(12) is bonded in a single-bond geometry to one C(26) atom. In the thirteenth H site, H(13) is bonded in a single-bond geometry to one C(28) atom. In the fourteenth H site, H(14) is bonded in a single-bond geometry to one C(29) atom. In the fifteenth H site, H(15) is bonded in a single-bond geometry to one C(31) atom. In the sixteenth H site, H(16) is bonded in a single-bond geometry to one C(32) atom. In the seventeenth H site, H(17) is bonded in a single-bond geometry to one C(32) atom. In the eighteenth H site, H(18) is bonded in a single-bond geometry to one C(32) atom. In the nineteenth H site, H(19) is bonded in a single-bond geometry to one C(33) atom. In the twentieth H site, H(20) is bonded in a single-bond geometry to one C(33) 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 linear geometry to one O(2) and one O(9) atom. The H(22)-O(2) bond length is 1.50 Å. The H(22)-O(9) bond length is 1.06 Å. In the twenty-third H site, H(23) is bonded in a single-bond geometry to one O(2) atom. The H(23)-O(2) bond length is 0.97 Å. In the twenty-fourth H site, H(24) is bonded in a linear geometry to one O(2) and one O(3) atom. The H(24)-O(2) bond length is 1.55 Å. The H(24)-O(3) bond length is 1.04 Å. In the twenty-fifth H site, H(25) is bonded in a single-bond geometry to one O(3) atom. The H(25)-O(3) bond length is 0.97 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded to one Zn(1), one Zn(2), one Zn(3), and one Zn(4) atom to form corner-sharing OZn4 tetrahedra. In the second O site, O(2) is bonded to one Zn(4), one H(22), one H(23), and one H(24) atom to form distorted corner-sharing OZnH3 tetrahedra. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Zn(3), one H(24), and one H(25) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Zn(1) and one C(7) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Zn(2) and one C(7) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Zn(3) and one C(8) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Zn(2) and one C(8) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Zn(4) and one C(15) atom. In the ninth O site, O(9) is bonded in a water-like geometry to one C(15) and one H(22) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Zn(1) and one C(22) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one Zn(4) and one C(22) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Zn(2) and one C(23) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 150 degrees geometry to one Zn(1) and one C(23) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one Zn(3) and one C(30) atom. In the fifteenth O site, O(15) is bonded in a bent 120 degrees geometry to one Zn(1) and one C(30) atom. In the sixteenth O site, O(16) is bonded in a bent 120 degrees geometry to one Zn(1) and one C(31) atom. Linkers: 4 [O]C(=O)c1cc(C([O])=O)cc(-c2ccc(C(=O)O)cc2)c1 ,4 [O]C(=O)c1ccc(-c2cc(C([O])=O)cc(C([O])=O)c2)cc1. Metal clusters: 4 CN(C)[CH]O[Zn]123O[C]O[Zn](O[C]O[Zn](O[C]O1)O[Zn@](O)(O[C]O)O[C]O2)O[C]O3.O. The MOF has largest included sphere 5.00 A, density 1.33 g/cm3, surface area 4024.32 m2/g, accessible volume 0.37 cm3/g