Mn5C48H24(N16O)2 crystallizes in the monoclinic C2/c space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a T-shaped geometry to one N(10), one N(7), and one O(1) atom. The Mn(1)-N(10) bond length is 2.24 Å. The Mn(1)-N(7) bond length is 2.25 Å. The Mn(1)-O(1) bond length is 2.21 Å. In the second Mn site, Mn(2) is bonded to one N(1), one N(11), one N(14), one N(5), and one O(1) atom to form corner-sharing MnN4O square pyramids. The corner-sharing octahedral tilt angles are 73°. The Mn(2)-N(1) bond length is 2.33 Å. The Mn(2)-N(11) bond length is 2.30 Å. The Mn(2)-N(14) bond length is 2.25 Å. The Mn(2)-N(5) bond length is 2.35 Å. The Mn(2)-O(1) bond length is 2.16 Å. In the third Mn site, Mn(3) is bonded to two equivalent N(2), two equivalent N(6), and two equivalent O(1) atoms to form corner-sharing MnN4O2 octahedra. Both Mn(3)-N(2) bond lengths are 2.22 Å. Both Mn(3)-N(6) bond lengths are 2.26 Å. Both Mn(3)-O(1) bond lengths are 2.15 Å. There are twenty-four inequivalent C sites. In the first C site, C(13) is bonded in a 2-coordinate geometry to one C(15), one N(12), and one N(9) atom. The C(13)-C(15) bond length is 1.47 Å. The C(13)-N(12) bond length is 1.33 Å. The C(13)-N(9) bond length is 1.34 Å. In the second C site, C(14) is bonded in a distorted trigonal planar geometry to one C(15), one C(23), and one H(7) atom. The C(14)-C(15) bond length is 1.43 Å. The C(14)-C(23) bond length is 1.36 Å. The C(14)-H(7) bond length is 0.95 Å. In the third C site, C(15) is bonded in a trigonal planar geometry to one C(13), one C(14), and one C(16) atom. The C(15)-C(16) bond length is 1.37 Å. In the fourth C site, C(16) is bonded in a distorted single-bond geometry to one C(15), one C(17), and one H(8) atom. The C(16)-C(17) bond length is 1.42 Å. The C(16)-H(8) bond length is 0.95 Å. In the fifth C site, C(17) is bonded in a trigonal planar geometry to one C(16), one C(18), and one C(22) atom. The C(17)-C(18) bond length is 1.43 Å. The C(17)-C(22) bond length is 1.41 Å. In the sixth C site, C(18) is bonded in a distorted single-bond geometry to one C(17) and one H(9) atom. The C(18)-H(9) bond length is 0.95 Å. In the seventh C site, C(19) is bonded in a distorted single-bond geometry to one C(20) and one H(10) atom. The C(19)-C(20) bond length is 1.42 Å. The C(19)-H(10) bond length is 0.95 Å. In the eighth C site, C(20) is bonded in a trigonal planar geometry to one C(19), one C(21), and one C(24) atom. The C(20)-C(21) bond length is 1.38 Å. The C(20)-C(24) bond length is 1.48 Å. In the ninth C site, C(21) is bonded in a distorted single-bond geometry to one C(20), one C(22), and one H(11) atom. The C(21)-C(22) bond length is 1.42 Å. The C(21)-H(11) bond length is 0.95 Å. In the tenth C site, C(22) is bonded in a trigonal planar geometry to one C(17), one C(21), and one C(23) atom. The C(22)-C(23) bond length is 1.43 Å. In the eleventh C site, C(23) is bonded in a distorted single-bond geometry to one C(14), one C(22), and one H(12) atom. The C(23)-H(12) bond length is 0.95 Å. In the twelfth C site, C(24) is bonded in a 2-coordinate geometry to one C(20), one N(13), and one N(16) atom. The C(24)-N(13) bond length is 1.31 Å. The C(24)-N(16) bond length is 1.34 Å. In the thirteenth C site, C(1) is bonded in a distorted trigonal planar geometry to one C(4), one N(1), and one N(4) atom. The C(1)-C(4) bond length is 1.48 Å. The C(1)-N(1) bond length is 1.34 Å. The C(1)-N(4) bond length is 1.35 Å. In the fourteenth C site, C(2) is bonded in a trigonal planar geometry to one C(2), one C(3), and one C(6) atom. The C(2)-C(2) bond length is 1.42 Å. The C(2)-C(3) bond length is 1.42 Å. The C(2)-C(6) bond length is 1.42 Å. In the fifteenth 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 1.38 Å. The C(3)-H(1) bond length is 0.95 Å. In the sixteenth C site, C(4) is bonded in a trigonal planar geometry to one C(1), one C(3), and one C(5) atom. The C(4)-C(5) bond length is 1.40 Å. In the seventeenth C site, C(5) is bonded in a single-bond geometry to one C(4) and one H(2) atom. The C(5)-H(2) bond length is 0.95 Å. In the eighteenth C site, C(6) is bonded in a distorted single-bond geometry to one C(2) and one H(3) atom. The C(6)-H(3) bond length is 0.95 Å. In the nineteenth C site, C(7) is bonded in a 2-coordinate geometry to one C(9), one N(5), and one N(8) atom. The C(7)-C(9) bond length is 1.48 Å. The C(7)-N(5) bond length is 1.34 Å. The C(7)-N(8) bond length is 1.33 Å. In the twentieth C site, C(8) is bonded in a single-bond geometry to one C(12), one C(9), and one H(4) atom. The C(8)-C(12) bond length is 1.42 Å. The C(8)-C(9) bond length is 1.37 Å. The C(8)-H(4) bond length is 0.95 Å. In the twenty-first C site, C(9) is bonded in a trigonal planar geometry to one C(10), one C(7), and one C(8) atom. The C(9)-C(10) bond length is 1.42 Å. In the twenty-second C site, C(10) is bonded in a distorted single-bond geometry to one C(9) and one H(5) atom. The C(10)-H(5) bond length is 0.95 Å. In the twenty-third C site, C(11) is bonded in a single-bond geometry to one C(12) and one H(6) atom. The C(11)-C(12) bond length is 1.42 Å. The C(11)-H(6) bond length is 0.95 Å. In the twenty-fourth C site, C(12) is bonded in a trigonal planar geometry to one C(11), one C(12), and one C(8) atom. The C(12)-C(12) bond length is 1.41 Å. There are sixteen inequivalent N sites. In the first N site, N(1) is bonded in a 3-coordinate geometry to one Mn(2), one C(1), and one N(2) atom. The N(1)-N(2) bond length is 1.36 Å. In the second N site, N(2) is bonded in a distorted trigonal planar geometry to one Mn(3), one N(1), and one N(3) atom. The N(2)-N(3) bond length is 1.32 Å. In the third N site, N(3) is bonded in a distorted water-like geometry to one N(2) and one N(4) atom. The N(3)-N(4) bond length is 1.33 Å. In the fourth N site, N(4) is bonded in a single-bond geometry to one C(1) and one N(3) atom. In the fifth N site, N(5) is bonded in a 3-coordinate geometry to one Mn(2), one C(7), and one N(6) atom. The N(5)-N(6) bond length is 1.34 Å. In the sixth N site, N(6) is bonded in a distorted trigonal planar geometry to one Mn(3), one N(5), and one N(7) atom. The N(6)-N(7) bond length is 1.32 Å. In the seventh N site, N(7) is bonded in a distorted trigonal planar geometry to one Mn(1), one N(6), and one N(8) atom. The N(7)-N(8) bond length is 1.34 Å. In the eighth N site, N(8) is bonded in a distorted single-bond geometry to one C(7) and one N(7) atom. In the ninth N site, N(9) is bonded in a distorted water-like geometry to one C(13) and one N(10) atom. The N(9)-N(10) bond length is 1.34 Å. In the tenth N site, N(10) is bonded in a distorted trigonal planar geometry to one Mn(1), one N(11), and one N(9) atom. The N(10)-N(11) bond length is 1.31 Å. In the eleventh N site, N(11) is bonded in a trigonal planar geometry to one Mn(2), one N(10), and one N(12) atom. The N(11)-N(12) bond length is 1.33 Å. In the twelfth N site, N(12) is bonded in a water-like geometry to one C(13) and one N(11) atom. In the thirteenth N site, N(13) is bonded in a water-like geometry to one C(24) and one N(14) atom. The N(13)-N(14) bond length is 1.34 Å. In the fourteenth N site, N(14) is bonded in a distorted trigonal planar geometry to one Mn(2), one N(13), and one N(15) atom. The N(14)-N(15) bond length is 1.31 Å. In the fifteenth N site, N(15) is bonded in a distorted water-like geometry to one N(14) and one N(16) atom. The N(15)-N(16) bond length is 1.34 Å. In the sixteenth N site, N(16) is bonded in a single-bond geometry to one C(24) and one N(15) atom. There are twelve inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(3) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(5) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(6) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(8) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(10) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(11) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(14) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(16) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(18) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one C(19) atom. In the eleventh H site, H(11) is bonded in a single-bond geometry to one C(21) atom. In the twelfth H site, H(12) is bonded in a single-bond geometry to one C(23) atom. O(1) is bonded in a trigonal non-coplanar geometry to one Mn(1), one Mn(2), and one Mn(3) atom. Linkers: 7 c1cc2cc(C3=NN=N[N]3)ccc2cc1C1=NN=N[N]1 ,1 c1cc2cc(C3=N[N]N=N3)ccc2cc1C1=NN=N[N]1. Metal clusters: 10 [Mn]. The MOF has largest included sphere 8.76 A, density 0.77 g/cm3, surface area 4236.13 m2/g, accessible volume 0.79 cm3/g