Na2Mn6C30N17H54O19 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one N(9), one O(11), one O(19), one O(2), one O(3), and one O(9) atom. The Na(1)-N(9) bond length is 2.42 Å. The Na(1)-O(11) bond length is 2.42 Å. The Na(1)-O(19) bond length is 2.44 Å. The Na(1)-O(2) bond length is 2.31 Å. The Na(1)-O(3) bond length is 2.30 Å. The Na(1)-O(9) bond length is 2.48 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one N(4), one H(31), one O(12), one O(15), one O(18), and one O(4) atom. The Na(2)-N(4) bond length is 2.36 Å. The Na(2)-H(31) bond length is 1.87 Å. The Na(2)-O(12) bond length is 2.56 Å. The Na(2)-O(15) bond length is 2.47 Å. The Na(2)-O(18) bond length is 2.47 Å. The Na(2)-O(4) bond length is 2.34 Å. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one N(7), one O(10), one O(17), one O(19), one O(7), and one O(9) atom to form a mixture of edge and corner-sharing MnNO5 octahedra. The corner-sharing octahedra are not tilted. The Mn(1)-N(7) bond length is 1.95 Å. The Mn(1)-O(10) bond length is 2.01 Å. The Mn(1)-O(17) bond length is 2.06 Å. The Mn(1)-O(19) bond length is 2.07 Å. The Mn(1)-O(7) bond length is 1.96 Å. The Mn(1)-O(9) bond length is 2.10 Å. In the second Mn site, Mn(2) is bonded to one N(5), one O(14), one O(15), one O(17), one O(18), and one O(7) atom to form a mixture of distorted edge and corner-sharing MnNO5 octahedra. The corner-sharing octahedral tilt angles are 7°. The Mn(2)-N(5) bond length is 2.13 Å. The Mn(2)-O(14) bond length is 1.93 Å. The Mn(2)-O(15) bond length is 1.93 Å. The Mn(2)-O(17) bond length is 1.96 Å. The Mn(2)-O(18) bond length is 1.94 Å. The Mn(2)-O(7) bond length is 2.30 Å. In the third Mn site, Mn(3) is bonded to one N(1), one O(11), one O(12), one O(18), one O(19), and one O(7) atom to form a mixture of edge and corner-sharing MnNO5 octahedra. The corner-sharing octahedral tilt angles are 6°. The Mn(3)-N(1) bond length is 2.02 Å. The Mn(3)-O(11) bond length is 2.07 Å. The Mn(3)-O(12) bond length is 1.92 Å. The Mn(3)-O(18) bond length is 2.09 Å. The Mn(3)-O(19) bond length is 1.92 Å. The Mn(3)-O(7) bond length is 2.28 Å. In the fourth Mn site, Mn(4) is bonded to one N(12), one O(12), one O(13), one O(15), one O(16), and one O(7) atom to form a mixture of distorted edge and corner-sharing MnNO5 octahedra. The corner-sharing octahedra are not tilted. The Mn(4)-N(12) bond length is 2.13 Å. The Mn(4)-O(12) bond length is 2.11 Å. The Mn(4)-O(13) bond length is 2.12 Å. The Mn(4)-O(15) bond length is 2.12 Å. The Mn(4)-O(16) bond length is 2.08 Å. The Mn(4)-O(7) bond length is 2.39 Å. In the fifth Mn site, Mn(5) is bonded to one N(10), one O(11), one O(13), one O(7), one O(8), and one O(9) atom to form a mixture of edge and corner-sharing MnNO5 octahedra. The corner-sharing octahedral tilt angles are 7°. The Mn(5)-N(10) bond length is 2.21 Å. The Mn(5)-O(11) bond length is 1.94 Å. The Mn(5)-O(13) bond length is 1.93 Å. The Mn(5)-O(7) bond length is 2.26 Å. The Mn(5)-O(8) bond length is 1.92 Å. The Mn(5)-O(9) bond length is 1.93 Å. In the sixth Mn site, Mn(6) is bonded to one N(13), one O(10), one O(14), one O(16), one O(7), and one O(8) atom to form a mixture of edge and corner-sharing MnNO5 octahedra. The corner-sharing octahedral tilt angles are 6°. The Mn(6)-N(13) bond length is 2.01 Å. The Mn(6)-O(10) bond length is 1.95 Å. The Mn(6)-O(14) bond length is 2.09 Å. The Mn(6)-O(16) bond length is 1.91 Å. The Mn(6)-O(7) bond length is 2.24 Å. The Mn(6)-O(8) bond length is 2.11 Å. There are thirty inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal non-coplanar geometry to one C(2); two equivalent H(1,2); and one O(8) atom. The C(1)-C(2) bond length is 1.53 Å. Both C(1)-H(1,2) bond lengths are 0.97 Å. The C(1)-O(8) bond length is 1.43 Å. In the second C site, C(2) is bonded in a tetrahedral geometry to one C(1), one C(3), one C(4), and one C(5) atom. The C(2)-C(3) bond length is 1.53 Å. The C(2)-C(4) bond length is 1.53 Å. The C(2)-C(5) bond length is 1.51 Å. In the third C site, C(3) is bonded in a distorted trigonal non-coplanar geometry to one C(2); two equivalent H(3,4); and one O(9) atom. Both C(3)-H(3,4) bond lengths are 0.97 Å. The C(3)-O(9) bond length is 1.44 Å. In the fourth C site, C(4) is bonded in a distorted trigonal non-coplanar geometry to one C(2); two equivalent H(5,6); and one O(10) atom. Both C(4)-H(5,6) bond lengths are 0.97 Å. The C(4)-O(10) bond length is 1.43 Å. In the fifth C site, C(5) is bonded in a trigonal non-coplanar geometry to one C(2); one H(9); and two equivalent H(7,8) atoms. The C(5)-H(9) bond length is 0.96 Å. Both C(5)-H(7,8) bond lengths are 0.96 Å. In the sixth C site, C(6) is bonded in a distorted trigonal non-coplanar geometry to one C(7), one H(10), one H(11), and one O(11) atom. The C(6)-C(7) bond length is 1.51 Å. The C(6)-H(10) bond length is 0.97 Å. The C(6)-H(11) bond length is 0.97 Å. The C(6)-O(11) bond length is 1.45 Å. In the seventh C site, C(7) is bonded to one C(10), one C(6), one C(8), and one C(9) atom to form CC4 tetrahedra that share  a cornercorner with one O(11)NaMn2C tetrahedra. The C(7)-C(10) bond length is 1.55 Å. The C(7)-C(8) bond length is 1.51 Å. The C(7)-C(9) bond length is 1.56 Å. In the eighth C site, C(8) is bonded in a distorted trigonal non-coplanar geometry to one C(7), one H(12), one H(13), and one O(12) atom. The C(8)-H(12) bond length is 0.97 Å. The C(8)-H(13) bond length is 0.97 Å. The C(8)-O(12) bond length is 1.42 Å. In the ninth C site, C(9) is bonded in a distorted trigonal non-coplanar geometry to one C(7); two equivalent H(14,15); and one O(13) atom. Both C(9)-H(14,15) bond lengths are 0.97 Å. The C(9)-O(13) bond length is 1.42 Å. In the tenth C site, C(10) is bonded in a trigonal non-coplanar geometry to one C(7); one H(18); and two equivalent H(16,17) atoms. The C(10)-H(18) bond length is 0.96 Å. Both C(10)-H(16,17) bond lengths are 0.96 Å. In the eleventh C site, C(11) is bonded in a distorted single-bond geometry to one C(12) and one O(14) atom. The C(11)-C(12) bond length is 1.52 Å. The C(11)-O(14) bond length is 1.45 Å. In the twelfth C site, C(12) is bonded to one C(11), one C(13), one C(14), and one C(15) atom to form CC4 tetrahedra that share  a cornercorner with one O(15)NaMn2C tetrahedra. The C(12)-C(13) bond length is 1.52 Å. The C(12)-C(14) bond length is 1.56 Å. The C(12)-C(15) bond length is 1.54 Å. In the thirteenth C site, C(13) is bonded in a distorted single-bond geometry to one C(12) and one O(15) atom. The C(13)-O(15) bond length is 1.46 Å. In the fourteenth C site, C(14) is bonded in a distorted single-bond geometry to one C(12) and one O(16) atom. The C(14)-O(16) bond length is 1.46 Å. In the fifteenth C site, C(15) is bonded in a trigonal non-coplanar geometry to one C(12); one H(20); and two equivalent H(19,21) atoms. The C(15)-H(20) bond length is 0.96 Å. Both C(15)-H(19,21) bond lengths are 0.96 Å. In the sixteenth C site, C(16) is bonded in a distorted trigonal non-coplanar geometry to one C(17); two equivalent H(22,23); and one O(17) atom. The C(16)-C(17) bond length is 1.52 Å. Both C(16)-H(22,23) bond lengths are 0.97 Å. The C(16)-O(17) bond length is 1.43 Å. In the seventeenth C site, C(17) is bonded to one C(16), one C(18), one C(19), and one C(20) atom to form CC4 tetrahedra that share  a cornercorner with one O(18)NaMn2C tetrahedra and  a cornercorner with one O(19)NaMn2C tetrahedra. The C(17)-C(18) bond length is 1.52 Å. The C(17)-C(19) bond length is 1.52 Å. The C(17)-C(20) bond length is 1.53 Å. In the eighteenth C site, C(18) is bonded in a distorted trigonal non-coplanar geometry to one C(17), one H(24), one H(25), and one O(18) atom. The C(18)-H(24) bond length is 0.97 Å. The C(18)-H(25) bond length is 0.97 Å. The C(18)-O(18) bond length is 1.45 Å. In the nineteenth C site, C(19) is bonded in a distorted trigonal non-coplanar geometry to one C(17); two equivalent H(26,27); and one O(19) atom. Both C(19)-H(26,27) bond lengths are 0.97 Å. The C(19)-O(19) bond length is 1.45 Å. In the twentieth C site, C(20) is bonded in a trigonal non-coplanar geometry to one C(17) and three equivalent H(28,29,30) atoms. All C(20)-H(28,29,30) bond lengths are 0.96 Å. In the twenty-first C site, C(21) is bonded in a distorted trigonal non-coplanar geometry to one C(22); two equivalent H(32,33); and one O(1) atom. The C(21)-C(22) bond length is 1.52 Å. Both C(21)-H(32,33) bond lengths are 0.97 Å. The C(21)-O(1) bond length is 1.44 Å. In the twenty-second C site, C(22) is bonded in a tetrahedral geometry to one C(21), one C(23), one C(24), and one C(25) atom. The C(22)-C(23) bond length is 1.52 Å. The C(22)-C(24) bond length is 1.50 Å. The C(22)-C(25) bond length is 1.53 Å. In the twenty-third C site, C(23) is bonded in a trigonal non-coplanar geometry to one C(22), one H(34), one H(35), and one H(36) atom. The C(23)-H(34) bond length is 0.96 Å. The C(23)-H(35) bond length is 0.96 Å. The C(23)-H(36) bond length is 0.96 Å. In the twenty-fourth C site, C(24) is bonded in a distorted trigonal non-coplanar geometry to one C(22), one H(37), one H(38), and one O(2) atom. The C(24)-H(37) bond length is 0.97 Å. The C(24)-H(38) bond length is 0.97 Å. The C(24)-O(2) bond length is 1.41 Å. In the twenty-fifth C site, C(25) is bonded in a distorted trigonal non-coplanar geometry to one C(22), one H(40), one H(41), and one O(5) atom. The C(25)-H(40) bond length is 0.97 Å. The C(25)-H(41) bond length is 0.97 Å. The C(25)-O(5) bond length is 1.39 Å. In the twenty-sixth C site, C(26) is bonded in a distorted trigonal non-coplanar geometry to one C(27); two equivalent H(43,44); and one O(3) atom. The C(26)-C(27) bond length is 1.52 Å. Both C(26)-H(43,44) bond lengths are 0.97 Å. The C(26)-O(3) bond length is 1.43 Å. In the twenty-seventh C site, C(27) is bonded in a tetrahedral geometry to one C(26), one C(28), one C(29), and one C(30) atom. The C(27)-C(28) bond length is 1.50 Å. The C(27)-C(29) bond length is 1.54 Å. The C(27)-C(30) bond length is 1.54 Å. In the twenty-eighth C site, C(28) is bonded in a distorted trigonal non-coplanar geometry to one C(27); two equivalent H(45,46); and one O(6) atom. Both C(28)-H(45,46) bond lengths are 0.97 Å. The C(28)-O(6) bond length is 1.41 Å. In the twenty-ninth C site, C(29) is bonded in a distorted trigonal non-coplanar geometry to one C(27); two equivalent H(48,49); and one O(4) atom. Both C(29)-H(48,49) bond lengths are 0.97 Å. The C(29)-O(4) bond length is 1.44 Å. In the thirtieth C site, C(30) is bonded in a trigonal non-coplanar geometry to one C(27); one H(52); and two equivalent H(53,54) atoms. The C(30)-H(52) bond length is 0.96 Å. Both C(30)-H(53,54) bond lengths are 0.96 Å. There are seventeen inequivalent N sites. In the first N site, N(1) is bonded in a distorted bent 120 degrees geometry to one Mn(3) and one N(2) atom. The N(1)-N(2) bond length is 1.18 Å. In the second N site, N(2) is bonded in a linear geometry to one N(1) and one N(3) atom. The N(2)-N(3) bond length is 1.16 Å. In the third N site, N(3) is bonded in a single-bond geometry to one N(2) atom. In the fourth N site, N(4) is bonded in a linear geometry to one Na(2) and one N(6) atom. The N(4)-N(6) bond length is 1.14 Å. In the fifth N site, N(5) is bonded in a bent 120 degrees geometry to one Mn(2) and one N(6) atom. The N(5)-N(6) bond length is 1.19 Å. In the sixth N site, N(6) is bonded in a linear geometry to one N(4) and one N(5) atom. In the seventh N site, N(7) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one N(8) atom. The N(7)-N(8) bond length is 1.20 Å. In the eighth N site, N(8) is bonded in a linear geometry to one N(7) and one N(9) atom. The N(8)-N(9) bond length is 1.15 Å. In the ninth N site, N(9) is bonded in a bent 150 degrees geometry to one Na(1) and one N(8) atom. In the tenth N site, N(10) is bonded in a bent 120 degrees geometry to one Mn(5) and one N(11) atom. The N(10)-N(11) bond length is 1.18 Å. In the eleventh N site, N(11) is bonded in a linear geometry to one N(10) and one N(12) atom. The N(11)-N(12) bond length is 1.18 Å. In the twelfth N site, N(12) is bonded in a distorted bent 150 degrees geometry to one Mn(4) and one N(11) atom. In the thirteenth N site, N(13) is bonded in a 3-coordinate geometry to one Mn(6), one N(14), and one N(16) atom. The N(13)-N(14) bond length is 0.96 Å. The N(13)-N(16) bond length is 0.85 Å. In the fourteenth N site, N(14) is bonded in a 3-coordinate geometry to one N(13), one N(15), and one N(16) atom. The N(14)-N(15) bond length is 1.28 Å. The N(14)-N(16) bond length is 0.85 Å. In the fifteenth N site, N(15) is bonded in a single-bond geometry to one N(14) atom. In the sixteenth N site, N(16) is bonded in a 3-coordinate geometry to one N(13), one N(14), and one N(17) atom. The N(16)-N(17) bond length is 1.26 Å. In the seventeenth N site, N(17) is bonded in a single-bond geometry to one N(16) atom. There are thirty-eight inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(3,4) is bonded in a single-bond geometry to one C(3) atom. In the third H site, H(5,6) is bonded in a single-bond geometry to one C(4) atom. In the fourth H site, H(7,8) is bonded in a single-bond geometry to one C(5) atom. In the fifth H site, H(9) is bonded in a single-bond geometry to one C(5) atom. In the sixth H site, H(10) is bonded in a single-bond geometry to one C(6) atom. In the seventh H site, H(11) is bonded in a single-bond geometry to one C(6) atom. In the eighth H site, H(12) is bonded in a single-bond geometry to one C(8) atom. In the ninth H site, H(13) is bonded in a single-bond geometry to one C(8) atom. In the tenth H site, H(14,15) is bonded in a single-bond geometry to one C(9) atom. In the eleventh H site, H(16,17) is bonded in a single-bond geometry to one C(10) atom. In the twelfth H site, H(18) is bonded in a single-bond geometry to one C(10) atom. In the thirteenth H site, H(19,21) is bonded in a single-bond geometry to one C(15) atom. In the fourteenth H site, H(20) is bonded in a single-bond geometry to one C(15) atom. In the fifteenth H site, H(22,23) is bonded in a single-bond geometry to one C(16) atom. In the sixteenth H site, H(24) is bonded in a single-bond geometry to one C(18) atom. In the seventeenth H site, H(25) is bonded in a single-bond geometry to one C(18) atom. In the eighteenth H site, H(26,27) is bonded in a single-bond geometry to one C(19) atom. In the nineteenth H site, H(28,29,30) is bonded in a single-bond geometry to one C(20) atom. In the twentieth H site, H(31) is bonded in a distorted single-bond geometry to one Na(2) and one O(1) atom. The H(31)-O(1) bond length is 0.82 Å. In the twenty-first H site, H(32,33) is bonded in a single-bond geometry to one C(21) atom. In the twenty-second H site, H(34) is bonded in a single-bond geometry to one C(23) atom. In the twenty-third H site, H(35) is bonded in a single-bond geometry to one C(23) atom. In the twenty-fourth H site, H(36) is bonded in a single-bond geometry to one C(23) atom. In the twenty-fifth H site, H(37) is bonded in a single-bond geometry to one C(24) atom. In the twenty-sixth H site, H(38) is bonded in a single-bond geometry to one C(24) atom. In the twenty-seventh H site, H(39) is bonded in a single-bond geometry to one O(2) atom. The H(39)-O(2) bond length is 0.82 Å. In the twenty-eighth H site, H(40) is bonded in a single-bond geometry to one C(25) atom. In the twenty-ninth H site, H(41) is bonded in a single-bond geometry to one C(25) atom. In the thirtieth H site, H(42) is bonded in a single-bond geometry to one O(3) atom. The H(42)-O(3) bond length is 0.82 Å. In the thirty-first H site, H(43,44) is bonded in a single-bond geometry to one C(26) atom. In the thirty-second H site, H(45,46) is bonded in a single-bond geometry to one C(28) atom. In the thirty-third H site, H(47) is bonded in a single-bond geometry to one O(4) atom. The H(47)-O(4) bond length is 0.82 Å. In the thirty-fourth H site, H(48,49) is bonded in a single-bond geometry to one C(29) atom. In the thirty-fifth H site, H(50) is bonded in a single-bond geometry to one O(5) atom. The H(50)-O(5) bond length is 0.82 Å. In the thirty-sixth H site, H(51) is bonded in a single-bond geometry to one O(6) atom. The H(51)-O(6) bond length is 0.82 Å. In the thirty-seventh H site, H(52) is bonded in a single-bond geometry to one C(30) atom. In the thirty-eighth H site, H(53,54) is bonded in a single-bond geometry to one C(30) atom. There are nineteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one C(21) and one H(31) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one C(24), and one H(39) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Na(1), one C(26), and one H(42) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(2), one C(29), and one H(47) atom. In the fifth O site, O(5) is bonded in a water-like geometry to one C(25) and one H(50) atom. In the sixth O site, O(6) is bonded in a water-like geometry to one C(28) and one H(51) atom. In the seventh O site, O(7) is bonded to one Mn(1), one Mn(2), one Mn(3), one Mn(4), one Mn(5), and one Mn(6) atom to form edge-sharing OMn6 octahedra. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to one Mn(5), one Mn(6), and one C(1) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Mn(1), one Mn(5), and one C(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(6), and one C(4) atom. In the eleventh O site, O(11) is bonded to one Na(1), one Mn(3), one Mn(5), and one C(6) atom to form distorted ONaMn2C tetrahedra that share  a cornercorner with one C(7)C4 tetrahedra,  a cornercorner with one O(18)NaMn2C tetrahedra,  an edgeedge with one O(7)Mn6 octahedra, and  an edgeedge with one O(19)NaMn2C tetrahedra. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Mn(3), one Mn(4), and one C(8) atom. In the thirteenth O site, O(13) is bonded in a trigonal non-coplanar geometry to one Mn(4), one Mn(5), and one C(9) atom. In the fourteenth O site, O(14) is bonded in a trigonal non-coplanar geometry to one Mn(2), one Mn(6), and one C(11) atom. In the fifteenth O site, O(15) is bonded to one Na(2), one Mn(2), one Mn(4), and one C(13) atom to form distorted ONaMn2C tetrahedra that share  a cornercorner with one C(12)C4 tetrahedra,  an edgeedge with one O(7)Mn6 octahedra, and  an edgeedge with one O(18)NaMn2C tetrahedra. In the sixteenth O site, O(16) is bonded in a trigonal non-coplanar geometry to one Mn(4), one Mn(6), and one C(14) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(2), and one C(16) atom. In the eighteenth O site, O(18) is bonded to one Na(2), one Mn(2), one Mn(3), and one C(18) atom to form distorted ONaMn2C tetrahedra that share  a cornercorner with one C(17)C4 tetrahedra,  a cornercorner with one O(11)NaMn2C tetrahedra,  a cornercorner with one O(19)NaMn2C tetrahedra,  an edgeedge with one O(7)Mn6 octahedra, and  an edgeedge with one O(15)NaMn2C tetrahedra. In the nineteenth O site, O(19) is bonded to one Na(1), one Mn(1), one Mn(3), and one C(19) atom to form distorted ONaMn2C tetrahedra that share  a cornercorner with one C(17)C4 tetrahedra,  a cornercorner with one O(18)NaMn2C tetrahedra,  an edgeedge with one O(7)Mn6 octahedra, and  an edgeedge with one O(11)NaMn2C tetrahedra. Linkers: 12 CC(C[O])(C[O])C[O] ,8 CC(CO)(CO)CO. Metal clusters: 8 [Na] ,24 [Mn]. The MOF has largest included sphere 4.89 A, density 1.61 g/cm3, surface area 3471.55 m2/g, accessible volume 0.25 cm3/g