Na5MnH24(C4O11)2 crystallizes in the monoclinic C2 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(8), two equivalent O(1), and two equivalent O(10) atoms to form distorted NaO5 trigonal bipyramids that share  a cornercorner with one Na(2)O6 octahedra and edges with two equivalent Na(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 64°. The Na(1)-O(8) bond length is 2.41 Å. There is one shorter (2.41 Å) and one longer (2.46 Å) Na(1)-O(1) bond length. There is one shorter (2.31 Å) and one longer (2.34 Å) Na(1)-O(10) bond length. In the second Na site, Na(2) is bonded to one O(2), one O(4), one O(5), one O(7), one O(8), and one O(9) atom to form distorted NaO6 octahedra that share  a cornercorner with one Na(1)O5 trigonal bipyramid and  an edgeedge with one Mn(1)O6 octahedra. The Na(2)-O(2) bond length is 2.81 Å. The Na(2)-O(4) bond length is 2.37 Å. The Na(2)-O(5) bond length is 2.39 Å. The Na(2)-O(7) bond length is 2.34 Å. The Na(2)-O(8) bond length is 2.32 Å. The Na(2)-O(9) bond length is 2.41 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent O(11), two equivalent O(5), and two equivalent O(9) atoms. Both Na(3)-O(11) bond lengths are 2.47 Å. Both Na(3)-O(5) bond lengths are 2.58 Å. Both Na(3)-O(9) bond lengths are 2.46 Å. Mn(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted MnO6 octahedra that share edges with two equivalent Na(2)O6 octahedra. Both Mn(1)-O(2) bond lengths are 2.33 Å. Both Mn(1)-O(3) bond lengths are 1.92 Å. Both Mn(1)-O(4) bond lengths are 1.93 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one O(1) and one O(2) atom. The C(1)-O(1) bond length is 1.25 Å. The C(1)-O(2) bond length is 1.29 Å. In the second C site, C(2) is bonded in a distorted water-like geometry to one H(1) and one O(3) atom. The C(2)-H(1) bond length is 1.10 Å. The C(2)-O(3) bond length is 1.44 Å. In the third C site, C(3) is bonded in a distorted water-like geometry to one H(2) and one O(4) atom. The C(3)-H(2) bond length is 1.11 Å. The C(3)-O(4) bond length is 1.42 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one O(5) and one O(6) atom. The C(4)-O(5) bond length is 1.28 Å. The C(4)-O(6) bond length is 1.27 Å. There are twelve 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 distorted single-bond geometry to one O(3) and one O(7) atom. The H(3)-O(3) bond length is 1.66 Å. The H(3)-O(7) bond length is 1.00 Å. In the fourth H site, H(4) is bonded in a distorted linear geometry to one O(4) and one O(7) atom. The H(4)-O(4) bond length is 1.60 Å. The H(4)-O(7) bond length is 1.01 Å. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(8) atom. The H(5)-O(8) bond length is 0.99 Å. In the sixth H site, H(6) is bonded in a single-bond geometry to one O(8) atom. The H(6)-O(8) bond length is 0.99 Å. In the seventh H site, H(7) is bonded in a distorted linear geometry to one O(3) and one O(9) atom. The H(7)-O(3) bond length is 1.66 Å. The H(7)-O(9) bond length is 1.01 Å. In the eighth H site, H(8) is bonded in a single-bond geometry to one O(9) atom. The H(8)-O(9) bond length is 0.97 Å. In the ninth H site, H(9) is bonded in a distorted linear geometry to one O(10) and one O(7) atom. The H(9)-O(10) bond length is 1.01 Å. The H(9)-O(7) bond length is 1.63 Å. In the tenth H site, H(10) is bonded in a single-bond geometry to one O(10) atom. The H(10)-O(10) bond length is 0.99 Å. In the eleventh H site, H(11) is bonded in a single-bond geometry to one O(11) atom. The H(11)-O(11) bond length is 1.00 Å. In the twelfth H site, H(12) is bonded in a single-bond geometry to one O(11) atom. The H(12)-O(11) bond length is 1.00 Å. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one C(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Na(2), one Mn(1), and one C(1) atom. In the third O site, O(3) is bonded to one Mn(1), one C(2), one H(3), and one H(7) atom to form distorted OMnH2C tetrahedra that share  a cornercorner with one O(3)MnH2C tetrahedra and corners with two equivalent O(4)NaMnHC tetrahedra. In the fourth O site, O(4) is bonded to one Na(2), one Mn(1), one C(3), and one H(4) atom to form distorted ONaMnHC tetrahedra that share  a cornercorner with one O(4)NaMnHC tetrahedra and corners with two equivalent O(3)MnH2C tetrahedra. In the fifth O site, O(5) is bonded in a 1-coordinate geometry to one Na(2), one Na(3), and one C(4) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one C(4) atom. In the seventh O site, O(7) is bonded in a distorted water-like geometry to one Na(2), one H(3), one H(4), and one H(9) atom. In the eighth O site, O(8) is bonded in a distorted water-like geometry to one Na(1), one Na(2), one H(5), and one H(6) atom. In the ninth O site, O(9) is bonded in a distorted water-like geometry to one Na(2), one Na(3), one H(7), and one H(8) atom. In the tenth O site, O(10) is bonded in a distorted water-like geometry to two equivalent Na(1), one H(10), and one H(9) atom. In the eleventh O site, O(11) is bonded in a water-like geometry to one Na(3), one H(11), and one H(12) atom. Linkers: 2 [O]C(=O)[C@H]([O])[C@@H]([O])C([O])=O. Metal clusters: 5 [Na] ,1 [Mn]. The MOF has largest included sphere 2.73 A, density 1.79 g/cm3, surface area 2574.11 m2/g, accessible volume 0.06 cm3/g