Mn3C64H61(N2O3)4 crystallizes in the orthorhombic Ama2 space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one N(1), one N(3), one O(1), one O(4), one O(5), and one O(6) atom to form distorted edge-sharing MnN2O4 pentagonal pyramids. The Mn(1)-N(1) bond length is 2.21 Å. The Mn(1)-N(3) bond length is 2.20 Å. The Mn(1)-O(1) bond length is 2.14 Å. The Mn(1)-O(4) bond length is 2.29 Å. The Mn(1)-O(5) bond length is 2.22 Å. The Mn(1)-O(6) bond length is 2.31 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted edge-sharing MnO8 hexagonal bipyramids. Both Mn(2)-O(1) bond lengths are 2.49 Å. Both Mn(2)-O(2) bond lengths are 2.22 Å. Both Mn(2)-O(3) bond lengths are 2.50 Å. Both Mn(2)-O(4) bond lengths are 2.21 Å. There are thirty-four inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(2), one O(1), and one O(2) atom. The C(1)-C(2) bond length is 1.49 Å. The C(1)-O(1) bond length is 1.26 Å. The C(1)-O(2) bond length is 1.25 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(3), and one C(7) atom. The C(2)-C(3) bond length is 1.38 Å. The C(2)-C(7) bond length is 1.39 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(2), one C(4), and one H(1) atom. The C(3)-C(4) bond length is 1.40 Å. The C(3)-H(1) bond length is 0.93 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(3), one C(5), and one C(9) atom. The C(4)-C(5) bond length is 1.40 Å. The C(4)-C(9) bond length is 1.52 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(2) atom. The C(5)-C(6) bond length is 1.38 Å. The C(5)-H(2) bond length is 0.93 Å. In the sixth C site, C(6) is bonded in a trigonal planar geometry to one C(5), one C(7), and one C(8) atom. The C(6)-C(7) bond length is 1.39 Å. The C(6)-C(8) bond length is 1.50 Å. In the seventh C site, C(7) is bonded in a distorted single-bond geometry to one C(2), one C(6), and one H(3) atom. The C(7)-H(3) bond length is 0.93 Å. In the eighth C site, C(8) is bonded in a bent 120 degrees geometry to one C(6), one O(3), and one O(4) atom. The C(8)-O(3) bond length is 1.23 Å. The C(8)-O(4) bond length is 1.27 Å. In the ninth C site, C(9) is bonded in a tetrahedral geometry to one C(28), one C(29), one C(30), and one C(4) atom. The C(9)-C(28) bond length is 1.52 Å. The C(9)-C(29) bond length is 1.54 Å. The C(9)-C(30) bond length is 1.50 Å. In the tenth C site, C(10) is bonded in a bent 120 degrees geometry to one C(11), one O(5), and one O(6) atom. The C(10)-C(11) bond length is 1.49 Å. The C(10)-O(5) bond length is 1.26 Å. The C(10)-O(6) bond length is 1.25 Å. In the eleventh C site, C(21) is bonded in a trigonal planar geometry to one C(20), one C(22), and one C(24) atom. The C(21)-C(20) bond length is 1.36 Å. The C(21)-C(22) bond length is 1.35 Å. The C(21)-C(24) bond length is 1.53 Å. In the twelfth C site, C(25) is bonded in a trigonal planar geometry to one N(3), one N(4), and one H(19) atom. The C(25)-N(3) bond length is 1.32 Å. The C(25)-N(4) bond length is 1.35 Å. The C(25)-H(19) bond length is 0.93 Å. In the thirteenth C site, C(26) is bonded in a distorted bent 120 degrees geometry to one C(27), one N(3), and one H(20) atom. The C(26)-C(27) bond length is 1.34 Å. The C(26)-N(3) bond length is 1.37 Å. The C(26)-H(20) bond length is 0.93 Å. In the fourteenth C site, C(29) is bonded in a trigonal non-coplanar geometry to one C(9); one H(27); and two equivalent H(22,23,25,26,28,30) atoms. The C(29)-H(27) bond length is 0.96 Å. Both C(29)-H(22,23,25,26,28,30) bond lengths are 0.96 Å. In the fifteenth C site, C(27) is bonded in a distorted bent 120 degrees geometry to one C(26), one N(4), and one H(21) atom. The C(27)-N(4) bond length is 1.37 Å. The C(27)-H(21) bond length is 0.93 Å. In the sixteenth C site, C(11) is bonded in a trigonal planar geometry to one C(10), one C(12), and one C(31) atom. The C(11)-C(12) bond length is 1.39 Å. The C(11)-C(31) bond length is 1.39 Å. In the seventeenth C site, C(12) is bonded in a single-bond geometry to one C(11), one C(32), and one H(4) atom. The C(12)-C(32) bond length is 1.39 Å. The C(12)-H(4) bond length is 0.93 Å. In the eighteenth C site, C(13) is bonded in a trigonal non-coplanar geometry to one C(33); one H(5); and two equivalent H(6,7) atoms. The C(13)-C(33) bond length is 1.48 Å. The C(13)-H(5) bond length is 0.96 Å. Both C(13)-H(6,7) bond lengths are 0.96 Å. In the nineteenth C site, C(14) is bonded in a distorted bent 120 degrees geometry to one C(15), one N(1), and one H(8) atom. The C(14)-C(15) bond length is 1.34 Å. The C(14)-N(1) bond length is 1.37 Å. The C(14)-H(8) bond length is 0.93 Å. In the twentieth C site, C(15) is bonded in a 3-coordinate geometry to one C(14), one N(2), and one H(9) atom. The C(15)-N(2) bond length is 1.38 Å. The C(15)-H(9) bond length is 0.93 Å. In the twenty-first C site, C(28) is bonded in a trigonal non-coplanar geometry to one C(9); one H(24,29); and two equivalent H(22,23,25,26,28,30) atoms. The C(28)-H(24,29) bond length is 0.96 Å. Both C(28)-H(22,23,25,26,28,30) bond lengths are 0.96 Å. In the twenty-second C site, C(30) is bonded in a trigonal non-coplanar geometry to one C(9); one H(24,29); and two equivalent H(22,23,25,26,28,30) atoms. The C(30)-H(24,29) bond length is 0.96 Å. Both C(30)-H(22,23,25,26,28,30) bond lengths are 0.96 Å. In the twenty-third C site, C(16) is bonded in a trigonal planar geometry to one N(1), one N(2), and one H(10) atom. The C(16)-N(1) bond length is 1.31 Å. The C(16)-N(2) bond length is 1.33 Å. The C(16)-H(10) bond length is 0.93 Å. In the twenty-fourth C site, C(17) is bonded in a 3-coordinate geometry to one C(18), one N(2), one H(11), and one H(12) atom. The C(17)-C(18) bond length is 1.51 Å. The C(17)-N(2) bond length is 1.47 Å. The C(17)-H(11) bond length is 0.97 Å. The C(17)-H(12) bond length is 0.97 Å. In the twenty-fifth 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 1.35 Å. The C(18)-C(23) bond length is 1.34 Å. In the twenty-sixth C site, C(19) is bonded in a distorted single-bond geometry to one C(18) and one H(13) atom. The C(19)-H(13) bond length is 0.93 Å. In the twenty-seventh C site, C(20) is bonded in a distorted single-bond geometry to one C(21) and one H(14) atom. The C(20)-H(14) bond length is 0.93 Å. In the twenty-eighth C site, C(22) is bonded in a distorted single-bond geometry to one C(21) and one H(15) atom. The C(22)-H(15) bond length is 0.93 Å. In the twenty-ninth C site, C(23) is bonded in a distorted single-bond geometry to one C(18) and one H(16) atom. The C(23)-H(16) bond length is 0.93 Å. In the thirtieth C site, C(31) is bonded in a distorted single-bond geometry to two equivalent C(11) and one H(31) atom. The C(31)-H(31) bond length is 0.93 Å. In the thirty-first C site, C(32) is bonded in a trigonal planar geometry to one C(33) and two equivalent C(12) atoms. The C(32)-C(33) bond length is 1.52 Å. In the thirty-second C site, C(33) is bonded in a tetrahedral geometry to one C(32), one C(34), and two equivalent C(13) atoms. The C(33)-C(34) bond length is 1.50 Å. In the thirty-third C site, C(34) is bonded in a single-bond geometry to one C(33) atom. In the thirty-fourth C site, C(24) is bonded in a 3-coordinate geometry to one C(21); one N(4); and two equivalent H(17,18) atoms. The C(24)-N(4) bond length is 1.44 Å. Both C(24)-H(17,18) bond lengths are 0.97 Å. There are four inequivalent N sites. In the first N site, N(4) is bonded in a trigonal planar geometry to one C(24), one C(25), and one C(27) atom. In the second N site, N(3) is bonded in a trigonal planar geometry to one Mn(1), one C(25), and one C(26) atom. In the third N site, N(1) is bonded in a distorted trigonal planar geometry to one Mn(1), one C(14), and one C(16) atom. In the fourth N site, N(2) is bonded in a trigonal planar geometry to one C(15), one C(16), and one C(17) atom. There are twenty-three inequivalent H sites. In the first H site, H(31) is bonded in a single-bond geometry to one C(31) atom. In the second H site, H(1) is bonded in a single-bond geometry to one C(3) atom. In the third H site, H(2) is bonded in a single-bond geometry to one C(5) atom. In the fourth H site, H(3) is bonded in a single-bond geometry to one C(7) atom. In the fifth H site, H(4) is bonded in a single-bond geometry to one C(12) atom. In the sixth H site, H(5) is bonded in a single-bond geometry to one C(13) atom. In the seventh H site, H(6,7) is bonded in a single-bond geometry to one C(13) 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(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(17) atom. In the thirteenth H site, H(13) is bonded in a single-bond geometry to one C(19) atom. In the fourteenth H site, H(14) is bonded in a single-bond geometry to one C(20) atom. In the fifteenth H site, H(15) is bonded in a single-bond geometry to one C(22) atom. In the sixteenth H site, H(16) is bonded in a single-bond geometry to one C(23) atom. In the seventeenth H site, H(17,18) is bonded in a single-bond geometry to one C(24) atom. In the eighteenth H site, H(19) is bonded in a single-bond geometry to one C(25) atom. In the nineteenth H site, H(20) is bonded in a single-bond geometry to one C(26) atom. In the twentieth H site, H(21) is bonded in a single-bond geometry to one C(27) atom. In the twenty-first H site, H(22,23,25,26,28,30) is bonded in a single-bond geometry to one C(28) atom. In the twenty-second H site, H(24,29) is bonded in a single-bond geometry to one C(28) atom. In the twenty-third H site, H(27) is bonded in a single-bond geometry to one C(29) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one C(1) atom. In the second O site, O(2) is bonded in a water-like geometry to one Mn(2) and one C(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Mn(2) and one C(8) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one C(8) atom. In the fifth O site, O(5) is bonded in a distorted L-shaped geometry to one Mn(1) and one C(10) atom. In the sixth O site, O(6) is bonded in a distorted L-shaped geometry to one Mn(1) and one C(10) atom. Linkers: 4 c1cn(Cc2ccc(Cn3ccnc3)cc2)cn1 ,4 CC(C)(C)c1cc(C([O])=O)cc(C([O])=O)c1 ,2 [C]C(C)(C)c1cc(C([O])=O)cc(C([O])=O)c1. Metal clusters: 2 O=[C]O[Mn](O[C]O[Mn]1O[C]O1)(O[C]O[Mn]1O[C]O1)O[C]=O. The MOF has largest included sphere 4.49 A, density 1.34 g/cm3, surface area 4868.59 m2/g, accessible volume 0.26 cm3/g