Na2Mn3H19(CO)13(CH3)3 crystallizes in the orthorhombic Pbcn space group. The structure consists of forty-eight 02329_fluka molecules inside a Na2Mn3H19(CO)13 framework. In the Na2Mn3H19(CO)13 framework, there are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted pentagonal planar geometry to one O(10), one O(3), one O(5), and two equivalent O(17) atoms. The Na(1)-O(10) bond length is 2.50 Å. The Na(1)-O(3) bond length is 2.37 Å. The Na(1)-O(5) bond length is 2.43 Å. There is one shorter (2.26 Å) and one longer (2.54 Å) Na(1)-O(17) bond length. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(12), one O(23), one O(4), one O(7), and two equivalent O(26) atoms. The Na(2)-O(12) bond length is 2.42 Å. The Na(2)-O(23) bond length is 2.30 Å. The Na(2)-O(4) bond length is 2.39 Å. The Na(2)-O(7) bond length is 2.57 Å. There is one shorter (2.37 Å) and one longer (2.39 Å) Na(2)-O(26) bond length. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(11), one O(15), one O(19), one O(21), one O(25), one O(6), and one O(9) atom. The Na(3)-O(11) bond length is 2.44 Å. The Na(3)-O(15) bond length is 2.90 Å. The Na(3)-O(19) bond length is 2.34 Å. The Na(3)-O(21) bond length is 2.39 Å. The Na(3)-O(25) bond length is 2.45 Å. The Na(3)-O(6) bond length is 2.50 Å. The Na(3)-O(9) bond length is 2.60 Å. In the fourth Na site, Na(4) is bonded to one O(13), one O(15), one O(19), one O(2), and one O(8) atom to form distorted NaO5 square pyramids that share  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, and  an edgeedge with one Mn(6)O6 octahedra. The Na(4)-O(13) bond length is 2.72 Å. The Na(4)-O(15) bond length is 2.24 Å. The Na(4)-O(19) bond length is 2.41 Å. The Na(4)-O(2) bond length is 2.37 Å. The Na(4)-O(8) bond length is 2.41 Å. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(10), one O(18), one O(2), one O(3), and one O(8) atom to form MnO6 octahedra that share  a cornercorner with one Mn(3)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one Mn(4)O6 octahedra,  an edgeedge with one Mn(5)O6 octahedra,  an edgeedge with one Mn(6)O6 octahedra, and  an edgeedge with one Na(4)O5 square pyramid. The corner-sharing octahedral tilt angles are 8°. The Mn(1)-O(1) bond length is 2.28 Å. The Mn(1)-O(10) bond length is 1.93 Å. The Mn(1)-O(18) bond length is 2.08 Å. The Mn(1)-O(2) bond length is 1.93 Å. The Mn(1)-O(3) bond length is 1.98 Å. The Mn(1)-O(8) bond length is 1.98 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(11), one O(13), one O(24), one O(8), and one O(9) atom to form MnO6 octahedra that share  a cornercorner with one Mn(5)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one Mn(4)O6 octahedra,  an edgeedge with one Mn(6)O6 octahedra, and  an edgeedge with one Na(4)O5 square pyramid. The corner-sharing octahedral tilt angles are 7°. The Mn(2)-O(1) bond length is 2.15 Å. The Mn(2)-O(11) bond length is 2.04 Å. The Mn(2)-O(13) bond length is 1.93 Å. The Mn(2)-O(24) bond length is 2.01 Å. The Mn(2)-O(8) bond length is 2.04 Å. The Mn(2)-O(9) bond length is 1.95 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(11), one O(12), one O(14), one O(6), and one O(7) atom to form a mixture of edge and corner-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 8°. The Mn(3)-O(1) bond length is 2.27 Å. The Mn(3)-O(11) bond length is 1.97 Å. The Mn(3)-O(12) bond length is 1.92 Å. The Mn(3)-O(14) bond length is 2.08 Å. The Mn(3)-O(6) bond length is 1.91 Å. The Mn(3)-O(7) bond length is 1.99 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(10), one O(20), one O(5), one O(6), and one O(9) atom to form a mixture of edge and corner-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 3°. The Mn(4)-O(1) bond length is 1.99 Å. The Mn(4)-O(10) bond length is 2.16 Å. The Mn(4)-O(20) bond length is 1.92 Å. The Mn(4)-O(5) bond length is 2.00 Å. The Mn(4)-O(6) bond length is 2.13 Å. The Mn(4)-O(9) bond length is 1.98 Å. In the fifth Mn site, Mn(5) is bonded to one O(1), one O(16), one O(3), one O(4), one O(5), and one O(7) atom to form a mixture of edge and corner-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 7°. The Mn(5)-O(1) bond length is 2.30 Å. The Mn(5)-O(16) bond length is 2.10 Å. The Mn(5)-O(3) bond length is 2.03 Å. The Mn(5)-O(4) bond length is 1.95 Å. The Mn(5)-O(5) bond length is 2.00 Å. The Mn(5)-O(7) bond length is 2.03 Å. In the sixth Mn site, Mn(6) is bonded to one O(1), one O(12), one O(13), one O(2), one O(22), and one O(4) atom to form distorted MnO6 octahedra that share  a cornercorner with one Mn(4)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one Mn(5)O6 octahedra, and  an edgeedge with one Na(4)O5 square pyramid. The corner-sharing octahedral tilt angles are 3°. The Mn(6)-O(1) bond length is 2.44 Å. The Mn(6)-O(12) bond length is 2.12 Å. The Mn(6)-O(13) bond length is 2.15 Å. The Mn(6)-O(2) bond length is 2.09 Å. The Mn(6)-O(22) bond length is 2.02 Å. The Mn(6)-O(4) bond length is 2.08 Å. There are twenty-six inequivalent C sites. In the first C site, C(1) is bonded to one C(2), one C(3), one C(4), and one C(5) atom to form CC4 tetrahedra that share  a cornercorner with one O(2)NaMn2C tetrahedra,  a cornercorner with one O(3)NaMn2C tetrahedra, and  a cornercorner with one O(4)NaMn2C tetrahedra. The C(1)-C(2) bond length is 1.54 Å. The C(1)-C(3) bond length is 1.52 Å. The C(1)-C(4) bond length is 1.52 Å. The C(1)-C(5) bond length is 1.54 Å. In the second C site, C(2) is bonded in a distorted trigonal non-coplanar geometry to one C(1); two equivalent H(1,2); and one O(2) atom. Both C(2)-H(1,2) bond lengths are 0.99 Å. The C(2)-O(2) bond length is 1.43 Å. In the third C site, C(3) is bonded in a distorted trigonal non-coplanar geometry to one C(1); two equivalent H(3,4); and one O(3) atom. Both C(3)-H(3,4) bond lengths are 0.99 Å. The C(3)-O(3) bond length is 1.43 Å. In the fourth C site, C(4) is bonded in a distorted trigonal non-coplanar geometry to one C(1), one H(5), one H(6), and one O(4) atom. The C(4)-H(5) bond length is 0.99 Å. The C(4)-H(6) bond length is 0.99 Å. The C(4)-O(4) bond length is 1.42 Å. In the fifth C site, C(5) is bonded in a trigonal non-coplanar geometry to one C(1), one H(7), one H(8), and one H(9) atom. The C(5)-H(7) bond length is 0.98 Å. The C(5)-H(8) bond length is 0.98 Å. The C(5)-H(9) bond length is 0.98 Å. In the sixth C site, C(6) is bonded to one C(10), one C(7), one C(8), and one C(9) atom to form CC4 tetrahedra that share  a cornercorner with one O(5)NaMn2C tetrahedra. The C(6)-C(10) bond length is 1.54 Å. The C(6)-C(7) bond length is 1.52 Å. The C(6)-C(8) bond length is 1.52 Å. The C(6)-C(9) bond length is 1.52 Å. In the seventh C site, C(7) is bonded in a distorted trigonal non-coplanar geometry to one C(6), one H(10), one H(11), and one O(5) atom. The C(7)-H(10) bond length is 0.99 Å. The C(7)-H(11) bond length is 0.99 Å. The C(7)-O(5) bond length is 1.44 Å. In the eighth C site, C(8) is bonded in a distorted trigonal non-coplanar geometry to one C(6); two equivalent H(12,13); and one O(6) atom. Both C(8)-H(12,13) bond lengths are 0.99 Å. The C(8)-O(6) 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(6), one H(14), one H(15), and one O(7) atom. The C(9)-H(14) bond length is 0.99 Å. The C(9)-H(15) bond length is 0.99 Å. The C(9)-O(7) bond length is 1.44 Å. In the tenth C site, C(10) is bonded in a trigonal non-coplanar geometry to one C(6); one H(18); and two equivalent H(16,17) atoms. The C(10)-H(18) bond length is 0.98 Å. Both C(10)-H(16,17) bond lengths are 0.98 Å. In the eleventh C site, C(11) is bonded to one C(12), one C(13), one C(14), and one C(15) atom to form CC4 tetrahedra that share  a cornercorner with one O(8)NaMn2C tetrahedra. The C(11)-C(12) bond length is 1.51 Å. The C(11)-C(13) bond length is 1.52 Å. The C(11)-C(14) bond length is 1.53 Å. The C(11)-C(15) bond length is 1.54 Å. In the twelfth C site, C(12) is bonded in a distorted trigonal non-coplanar geometry to one C(11); two equivalent H(19,20); and one O(8) atom. Both C(12)-H(19,20) bond lengths are 0.99 Å. The C(12)-O(8) bond length is 1.43 Å. In the thirteenth C site, C(13) is bonded in a distorted trigonal non-coplanar geometry to one C(11), one H(21), one H(22), and one O(9) atom. The C(13)-H(21) bond length is 0.99 Å. The C(13)-H(22) bond length is 0.99 Å. The C(13)-O(9) bond length is 1.45 Å. In the fourteenth C site, C(14) is bonded in a distorted trigonal non-coplanar geometry to one C(11); two equivalent H(23,24); and one O(10) atom. Both C(14)-H(23,24) bond lengths are 0.99 Å. The C(14)-O(10) bond length is 1.43 Å. In the fifteenth C site, C(15) is bonded in a trigonal non-coplanar geometry to one C(11) and three equivalent H(25,26,27) atoms. All C(15)-H(25,26,27) bond lengths are 0.98 Å. In the sixteenth C site, C(16) is bonded to one C(17), one C(18), one C(19), and one C(20) atom to form CC4 tetrahedra that share  a cornercorner with one O(11)NaMn2C tetrahedra and  a cornercorner with one O(12)NaMn2C tetrahedra. The C(16)-C(17) bond length is 1.51 Å. The C(16)-C(18) bond length is 1.53 Å. The C(16)-C(19) bond length is 1.54 Å. The C(16)-C(20) bond length is 1.52 Å. In the seventeenth C site, C(17) is bonded in a distorted trigonal non-coplanar geometry to one C(16); two equivalent H(28,29); and one O(11) atom. Both C(17)-H(28,29) bond lengths are 0.99 Å. The C(17)-O(11) bond length is 1.44 Å. In the eighteenth C site, C(18) is bonded in a distorted trigonal non-coplanar geometry to one C(16), one H(30), one H(31), and one O(12) atom. The C(18)-H(30) bond length is 0.99 Å. The C(18)-H(31) bond length is 0.99 Å. The C(18)-O(12) bond length is 1.43 Å. In the nineteenth C site, C(19) is bonded in a distorted trigonal non-coplanar geometry to one C(16); two equivalent H(32,33); and one O(13) atom. Both C(19)-H(32,33) bond lengths are 0.99 Å. The C(19)-O(13) bond length is 1.43 Å. In the twentieth C site, C(20) is bonded in a trigonal non-coplanar geometry to one C(16) and three equivalent H(34,35,36) atoms. All C(20)-H(34,35,36) bond lengths are 0.98 Å. In the twenty-first C site, C(21) is bonded in a distorted bent 120 degrees geometry to one O(14) and one O(15) atom. The C(21)-O(14) bond length is 1.29 Å. The C(21)-O(15) bond length is 1.22 Å. In the twenty-second C site, C(23) is bonded in a distorted bent 120 degrees geometry to one O(16) and one O(17) atom. The C(23)-O(16) bond length is 1.29 Å. The C(23)-O(17) bond length is 1.24 Å. In the twenty-third C site, C(25) is bonded in a distorted bent 120 degrees geometry to one O(18) and one O(19) atom. The C(25)-O(18) bond length is 1.29 Å. The C(25)-O(19) bond length is 1.24 Å. In the twenty-fourth C site, C(27) is bonded in a distorted bent 120 degrees geometry to one O(20) and one O(21) atom. The C(27)-O(20) bond length is 1.32 Å. The C(27)-O(21) bond length is 1.23 Å. In the twenty-fifth C site, C(29) is bonded in a distorted bent 120 degrees geometry to one O(22) and one O(23) atom. The C(29)-O(22) bond length is 1.24 Å. The C(29)-O(23) bond length is 1.34 Å. In the twenty-sixth C site, C(31) is bonded in a distorted bent 120 degrees geometry to one O(24) and one O(25) atom. The C(31)-O(24) bond length is 1.29 Å. The C(31)-O(25) bond length is 1.22 Å. There are twenty-six inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one C(2) 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) is bonded in a single-bond geometry to one C(4) atom. In the fourth H site, H(6) is bonded in a single-bond geometry to one C(4) atom. In the fifth H site, H(7) is bonded in a single-bond geometry to one C(5) atom. In the sixth H site, H(8) is bonded in a single-bond geometry to one C(5) atom. In the seventh H site, H(9) is bonded in a single-bond geometry to one C(5) atom. In the eighth H site, H(10) is bonded in a single-bond geometry to one C(7) atom. In the ninth H site, H(11) is bonded in a single-bond geometry to one C(7) atom. In the tenth H site, H(12,13) is bonded in a single-bond geometry to one C(8) atom. In the eleventh H site, H(14) is bonded in a single-bond geometry to one C(9) atom. In the twelfth H site, H(15) is bonded in a single-bond geometry to one C(9) atom. In the thirteenth H site, H(16,17) is bonded in a single-bond geometry to one C(10) atom. In the fourteenth H site, H(18) is bonded in a single-bond geometry to one C(10) atom. In the fifteenth H site, H(19,20) is bonded in a single-bond geometry to one C(12) atom. In the sixteenth H site, H(21) is bonded in a single-bond geometry to one C(13) atom. In the seventeenth H site, H(22) is bonded in a single-bond geometry to one C(13) atom. In the eighteenth H site, H(23,24) is bonded in a single-bond geometry to one C(14) atom. In the nineteenth H site, H(25,26,27) is bonded in a single-bond geometry to one C(15) atom. In the twentieth H site, H(28,29) is bonded in a single-bond geometry to one C(17) atom. In the twenty-first H site, H(30) is bonded in a single-bond geometry to one C(18) atom. In the twenty-second H site, H(31) is bonded in a single-bond geometry to one C(18) atom. In the twenty-third H site, H(32,33) is bonded in a single-bond geometry to one C(19) atom. In the twenty-fourth H site, H(34,35,36) is bonded in a single-bond geometry to one C(20) atom. In the twenty-fifth H site, H(55) is bonded in a single-bond geometry to one O(26) atom. The H(55)-O(26) bond length is 0.84 Å. In the twenty-sixth H site, H(56) is bonded in a single-bond geometry to one O(26) atom. The H(56)-O(26) bond length is 0.84 Å. There are twenty-six inequivalent O sites. In the first O site, O(1) 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 second O site, O(2) is bonded to one Na(4), one Mn(1), one Mn(6), and one C(2) atom to form distorted ONaMn2C tetrahedra that share  a cornercorner with one C(1)C4 tetrahedra,  a cornercorner with one O(12)NaMn2C tetrahedra,  a cornercorner with one O(3)NaMn2C tetrahedra,  a cornercorner with one O(4)NaMn2C tetrahedra,  an edgeedge with one O(1)Mn6 octahedra, and  an edgeedge with one O(8)NaMn2C tetrahedra. In the third O site, O(3) is bonded to one Na(1), one Mn(1), one Mn(5), and one C(3) atom to form distorted ONaMn2C tetrahedra that share  a cornercorner with one C(1)C4 tetrahedra,  a cornercorner with one O(2)NaMn2C tetrahedra,  a cornercorner with one O(4)NaMn2C tetrahedra,  a cornercorner with one O(8)NaMn2C tetrahedra,  an edgeedge with one O(1)Mn6 octahedra, and  an edgeedge with one O(5)NaMn2C tetrahedra. In the fourth O site, O(4) is bonded to one Na(2), one Mn(5), one Mn(6), and one C(4) atom to form distorted ONaMn2C tetrahedra that share  a cornercorner with one C(1)C4 tetrahedra,  a cornercorner with one O(2)NaMn2C tetrahedra,  a cornercorner with one O(3)NaMn2C tetrahedra,  a cornercorner with one O(5)NaMn2C tetrahedra,  an edgeedge with one O(1)Mn6 octahedra, and  an edgeedge with one O(12)NaMn2C tetrahedra. In the fifth O site, O(5) is bonded to one Na(1), one Mn(4), one Mn(5), and one C(7) atom to form distorted ONaMn2C tetrahedra that share  a cornercorner with one C(6)C4 tetrahedra,  a cornercorner with one O(4)NaMn2C tetrahedra,  an edgeedge with one O(1)Mn6 octahedra, and  an edgeedge with one O(3)NaMn2C tetrahedra. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(3), one Mn(3), one Mn(4), and one C(8) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Mn(3), one Mn(5), and one C(9) atom. In the eighth O site, O(8) is bonded to one Na(4), one Mn(1), one Mn(2), and one C(12) atom to form distorted ONaMn2C tetrahedra that share  a cornercorner with one C(11)C4 tetrahedra,  a cornercorner with one O(11)NaMn2C tetrahedra,  a cornercorner with one O(3)NaMn2C tetrahedra,  an edgeedge with one O(1)Mn6 octahedra, and  an edgeedge with one O(2)NaMn2C tetrahedra. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(3), one Mn(2), one Mn(4), and one C(13) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(1), one Mn(1), one Mn(4), and one C(14) atom. In the eleventh O site, O(11) is bonded to one Na(3), one Mn(2), one Mn(3), and one C(17) atom to form distorted ONaMn2C tetrahedra that share  a cornercorner with one C(16)C4 tetrahedra,  a cornercorner with one O(12)NaMn2C tetrahedra,  a cornercorner with one O(8)NaMn2C tetrahedra, and  an edgeedge with one O(1)Mn6 octahedra. In the twelfth O site, O(12) is bonded to one Na(2), one Mn(3), one Mn(6), and one C(18) atom to form distorted ONaMn2C tetrahedra that share  a cornercorner with one C(16)C4 tetrahedra,  a cornercorner with one O(11)NaMn2C tetrahedra,  a cornercorner with one O(2)NaMn2C tetrahedra,  an edgeedge with one O(1)Mn6 octahedra, and  an edgeedge with one O(4)NaMn2C tetrahedra. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Na(4), one Mn(2), one Mn(6), and one C(19) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one Mn(3) and one C(21) atom. In the fifteenth O site, O(15) is bonded in a 1-coordinate geometry to one Na(3), one Na(4), and one C(21) atom. In the sixteenth O site, O(16) is bonded in a bent 120 degrees geometry to one Mn(5) and one C(23) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one C(23) atom. In the eighteenth O site, O(18) is bonded in a bent 120 degrees geometry to one Mn(1) and one C(25) atom. In the nineteenth O site, O(19) is bonded in a distorted single-bond geometry to one Na(3), one Na(4), and one C(25) atom. In the twentieth O site, O(20) is bonded in a bent 120 degrees geometry to one Mn(4) and one C(27) atom. In the twenty-first O site, O(21) is bonded in a distorted bent 150 degrees geometry to one Na(3) and one C(27) atom. In the twenty-second O site, O(22) is bonded in a bent 120 degrees geometry to one Mn(6) and one C(29) atom. In the twenty-third O site, O(23) is bonded in a 2-coordinate geometry to one Na(2) and one C(29) atom. In the twenty-fourth O site, O(24) is bonded in a bent 120 degrees geometry to one Mn(2) and one C(31) atom. In the twenty-fifth O site, O(25) is bonded in a distorted single-bond geometry to one Na(3) and one C(31) atom. In the twenty-sixth O site, O(26) is bonded in a distorted water-like geometry to two equivalent Na(2), one H(55), and one H(56) atom. Linkers: 32 CC(C[O])(C[O])C[O]. Metal clusters: 32 [Na] ,48 [Mn]. The MOF has largest included sphere 5.16 A, density 1.37 g/cm3, surface area 3202.90 m2/g, accessible volume 0.35 cm3/g