Mn6Zn3C81H33(N3O16)2 crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(6), one O(7), and one O(8) atom. The Mn(1)-O(2) bond length is 2.17 Å. The Mn(1)-O(3) bond length is 2.28 Å. The Mn(1)-O(4) bond length is 2.15 Å. The Mn(1)-O(6) bond length is 2.28 Å. The Mn(1)-O(7) bond length is 2.21 Å. The Mn(1)-O(8) bond length is 2.10 Å. In the second Mn site, Mn(2) is bonded in an octahedral geometry to one O(8), one O(9), two equivalent O(1), and two equivalent O(5) atoms. The Mn(2)-O(8) bond length is 2.17 Å. The Mn(2)-O(9) bond length is 2.18 Å. Both Mn(2)-O(1) bond lengths are 2.15 Å. Both Mn(2)-O(5) bond lengths are 2.16 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a single-bond geometry to one Zn(1), two equivalent N(1), and two equivalent N(2) atoms. The Zn(1)-Zn(1) bond length is 0.72 Å. Both Zn(1)-N(1) bond lengths are 2.08 Å. Both Zn(1)-N(2) bond lengths are 2.08 Å. In the second Zn site, Zn(2) is bonded in a single-bond geometry to one Zn(2), one N(3), one N(4), and two equivalent N(5) atoms. The Zn(2)-Zn(2) bond length is 0.92 Å. The Zn(2)-N(3) bond length is 2.06 Å. The Zn(2)-N(4) bond length is 2.10 Å. Both Zn(2)-N(5) bond lengths are 2.08 Å. There are thirty-two inequivalent C sites. In the first C site, C(23) is bonded in a distorted single-bond geometry to one C(11) and one H(9) atom. The C(23)-C(11) bond length is 1.49 Å. The C(23)-H(9) bond length is 0.95 Å. In the second C site, C(24) is bonded in a distorted single-bond geometry to one C(12) and one H(10) atom. The C(24)-C(12) bond length is 1.45 Å. The C(24)-H(10) bond length is 0.95 Å. In the third C site, C(1) is bonded in a trigonal planar geometry to one C(29), one C(3), and one C(6) atom. The C(1)-C(29) bond length is 1.39 Å. The C(1)-C(3) bond length is 1.41 Å. The C(1)-C(6) bond length is 1.49 Å. In the fourth C site, C(2) is bonded in a distorted single-bond geometry to one C(13), one C(4), and one H(1) atom. The C(2)-C(13) bond length is 1.39 Å. The C(2)-C(4) bond length is 1.39 Å. The C(2)-H(1) bond length is 0.95 Å. In the fifth C site, C(3) is bonded in a distorted single-bond geometry to one C(1), one C(28), and one H(2) atom. The C(3)-C(28) bond length is 1.39 Å. The C(3)-H(2) bond length is 0.95 Å. In the sixth C site, C(4) is bonded in a trigonal planar geometry to one C(2), one C(20), and one C(8) atom. The C(4)-C(20) bond length is 1.38 Å. The C(4)-C(8) bond length is 1.51 Å. In the seventh C site, C(5) is bonded in a trigonal planar geometry to one C(22), one C(7), and one C(9) atom. The C(5)-C(22) bond length is 1.40 Å. The C(5)-C(7) bond length is 1.35 Å. The C(5)-C(9) bond length is 1.53 Å. In the eighth C site, C(6) is bonded in a distorted bent 120 degrees geometry to one C(1), one O(1), and one O(2) atom. The C(6)-O(1) bond length is 1.25 Å. The C(6)-O(2) bond length is 1.24 Å. In the ninth C site, C(7) is bonded in a distorted single-bond geometry to one C(17), one C(5), and one H(3) atom. The C(7)-C(17) bond length is 1.38 Å. The C(7)-H(3) bond length is 0.95 Å. In the tenth C site, C(8) is bonded in a bent 120 degrees geometry to one C(4), one O(4), and one O(5) atom. The C(8)-O(4) bond length is 1.24 Å. The C(8)-O(5) bond length is 1.23 Å. In the eleventh C site, C(9) is bonded in a bent 120 degrees geometry to one C(5), one O(3), and one O(6) atom. The C(9)-O(3) bond length is 1.24 Å. The C(9)-O(6) bond length is 1.25 Å. In the twelfth C site, C(25) is bonded in a distorted trigonal planar geometry to one C(27), one C(31), and one N(1) atom. The C(25)-C(27) bond length is 1.41 Å. The C(25)-C(31) bond length is 1.44 Å. The C(25)-N(1) bond length is 1.37 Å. In the thirteenth C site, C(26) is bonded in a distorted trigonal planar geometry to one C(27), one C(30), and one N(2) atom. The C(26)-C(27) bond length is 1.38 Å. The C(26)-C(30) bond length is 1.43 Å. The C(26)-N(2) bond length is 1.38 Å. In the fourteenth C site, C(27) is bonded in a trigonal planar geometry to one C(25), one C(26), and one C(28) atom. The C(27)-C(28) bond length is 1.50 Å. In the fifteenth C site, C(28) is bonded in a trigonal planar geometry to one C(27) and two equivalent C(3) atoms. In the sixteenth C site, C(29) is bonded in a distorted trigonal planar geometry to two equivalent C(1) and one H(11) atom. The C(29)-H(11) bond length is 0.95 Å. In the seventeenth C site, C(30) is bonded in a distorted single-bond geometry to one C(26) and one H(12) atom. The C(30)-H(12) bond length is 0.95 Å. In the eighteenth C site, C(31) is bonded in a distorted single-bond geometry to one C(25) and one H(13) atom. The C(31)-H(13) bond length is 0.95 Å. In the nineteenth C site, C(32) is bonded in a trigonal planar geometry to one H(14) and two equivalent O(9) atoms. The C(32)-H(14) bond length is 0.95 Å. Both C(32)-O(9) bond lengths are 1.27 Å. In the twentieth C site, C(10) is bonded in a trigonal planar geometry to one H(4) and two equivalent O(7) atoms. The C(10)-H(4) bond length is 0.95 Å. Both C(10)-O(7) bond lengths are 1.08 Å. In the twenty-first C site, C(11) is bonded in a distorted trigonal planar geometry to one C(14), one C(23), and one N(4) atom. The C(11)-C(14) bond length is 1.35 Å. The C(11)-N(4) bond length is 1.36 Å. In the twenty-second C site, C(12) is bonded in a distorted trigonal planar geometry to one C(14), one C(24), and one N(5) atom. The C(12)-C(14) bond length is 1.41 Å. The C(12)-N(5) bond length is 1.35 Å. In the twenty-third C site, C(13) is bonded in a trigonal planar geometry to one C(18) and two equivalent C(2) atoms. The C(13)-C(18) bond length is 1.45 Å. In the twenty-fourth C site, C(14) is bonded in a trigonal planar geometry to one C(11), one C(12), and one C(17) atom. The C(14)-C(17) bond length is 1.51 Å. In the twenty-fifth C site, C(15) is bonded in a distorted trigonal planar geometry to one C(18), one C(21), and one N(5) atom. The C(15)-C(18) bond length is 1.41 Å. The C(15)-C(21) bond length is 1.44 Å. The C(15)-N(5) bond length is 1.39 Å. In the twenty-sixth C site, C(16) is bonded in a distorted single-bond geometry to one C(19) and one H(5) atom. The C(16)-C(19) bond length is 1.44 Å. The C(16)-H(5) bond length is 0.95 Å. In the twenty-seventh C site, C(17) is bonded in a trigonal planar geometry to one C(14) and two equivalent C(7) atoms. In the twenty-eighth C site, C(18) is bonded in a trigonal planar geometry to one C(13), one C(15), and one C(19) atom. The C(18)-C(19) bond length is 1.38 Å. In the twenty-ninth C site, C(19) is bonded in a distorted trigonal planar geometry to one C(16), one C(18), and one N(3) atom. The C(19)-N(3) bond length is 1.42 Å. In the thirtieth C site, C(20) is bonded in a distorted trigonal planar geometry to two equivalent C(4) and one H(6) atom. The C(20)-H(6) bond length is 0.95 Å. In the thirty-first C site, C(21) is bonded in a distorted single-bond geometry to one C(15) and one H(7) atom. The C(21)-H(7) bond length is 0.95 Å. In the thirty-second C site, C(22) is bonded in a distorted trigonal planar geometry to two equivalent C(5) and one H(8) atom. The C(22)-H(8) bond length is 0.95 Å. There are five inequivalent N sites. In the first N site, N(5) is bonded in a 4-coordinate geometry to two equivalent Zn(2), one C(12), and one C(15) atom. In the second N site, N(1) is bonded in a 4-coordinate geometry to two equivalent Zn(1) and two equivalent C(25) atoms. In the third N site, N(2) is bonded in a distorted water-like geometry to two equivalent Zn(1) and two equivalent C(26) atoms. In the fourth N site, N(3) is bonded in a 4-coordinate geometry to two equivalent Zn(2) and two equivalent C(19) atoms. In the fifth N site, N(4) is bonded in a 4-coordinate geometry to two equivalent Zn(2) and two equivalent C(11) atoms. There are fourteen 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(3) 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(10) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(16) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(20) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(21) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(22) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(23) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one C(24) atom. In the eleventh H site, H(11) is bonded in a single-bond geometry to one C(29) atom. In the twelfth H site, H(12) is bonded in a single-bond geometry to one C(30) atom. In the thirteenth H site, H(13) is bonded in a single-bond geometry to one C(31) atom. In the fourteenth H site, H(14) is bonded in a single-bond geometry to one C(32) atom. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Mn(2) and one C(6) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Mn(1) and one C(6) atom. In the third O site, O(3) is bonded in an L-shaped geometry to one Mn(1) and one C(9) atom. In the fourth O site, O(4) is bonded in a water-like geometry to one Mn(1) and one C(8) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Mn(2) and one C(8) atom. In the sixth O site, O(6) is bonded in an L-shaped geometry to one Mn(1) and one C(9) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Mn(1) and one C(10) atom. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to one Mn(2) and two equivalent Mn(1) atoms. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one Mn(2) and one C(32) atom. Linkers: 6 [O]C(=O)c1cc(C([O])=O)cc(/C2=C3\C=C/C(=C(\c4cc(C([O])=O)cc(C([O])=O)c4)C4=N/C(=C(/c5cc(C([O])=O)cc(C([O])=O)c5)C5=CC=C([N]5)/C(c5cc(C([O])=O)cc(C([O])=O)c5)=C5/C=CC2=N5)C=C4)[N]3)c1. Metal clusters: 4 [C]1O[Mn]23(O[CH]O[Mn]456O[C]O[Mn]78(O[C]O4)(O[C]O7)O[CH]O[Mn]4(O[C]O5)(O[C]O6)(O[C]O4)O8)O[C]O[Mn]45(O1)(O[C]O4)O[CH]O[Mn]1(O[C]O2)(O[C]O3)(O[C]O1)O5 ,4 [N][Zn]([N])([N])([N])[Zn] ,1 [N][Zn]([N])[Zn]([N])[N] ,1 [N][Zn][Zn]([N])([N])[N]. The MOF has largest included sphere 8.30 A, density 0.95 g/cm3, surface area 3521.66 m2/g, accessible volume 0.66 cm3/g