MnCu8C52H20(N2O9)2 crystallizes in the hexagonal P6_3/mcm space group. Mn(1) is bonded in an octahedral geometry to two equivalent N(1), two equivalent N(2), and two equivalent O(5) atoms. Both Mn(1)-N(1) bond lengths are 2.02 Å. Both Mn(1)-N(2) bond lengths are 2.02 Å. Both Mn(1)-O(5) bond lengths are 2.30 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in an L-shaped geometry to one O(4) and one O(5) atom. The Cu(1)-O(4) bond length is 1.90 Å. The Cu(1)-O(5) bond length is 1.94 Å. In the second Cu site, Cu(2) is bonded in a T-shaped geometry to one O(5) and two equivalent O(3) atoms. The Cu(2)-O(5) bond length is 1.96 Å. Both Cu(2)-O(3) bond lengths are 1.91 Å. In the third Cu site, Cu(3) is bonded in a linear geometry to two equivalent O(2) atoms. Both Cu(3)-O(2) bond lengths are 1.93 Å. There are thirteen inequivalent C sites. In the first C site, C(1) is bonded in a distorted single-bond geometry to one C(2) and one H(1) atom. The C(1)-C(2) bond length is 1.42 Å. The C(1)-H(1) bond length is 0.93 Å. In the second C site, C(2) is bonded in a distorted trigonal planar geometry to one C(1), one C(3), and one N(1) atom. The C(2)-C(3) bond length is 1.39 Å. The C(2)-N(1) bond length is 1.39 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(2), one C(4), and one C(6) atom. The C(3)-C(4) bond length is 1.39 Å. The C(3)-C(6) bond length is 1.50 Å. In the fourth C site, C(4) is bonded in a distorted trigonal planar geometry to one C(3), one C(5), and one N(2) atom. The C(4)-C(5) bond length is 1.43 Å. The C(4)-N(2) bond length is 1.37 Å. In the fifth C site, C(5) is bonded in a distorted single-bond geometry to one C(4) and one H(2) atom. 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(11), one C(3), and one C(7) atom. The C(6)-C(11) bond length is 1.39 Å. The C(6)-C(7) bond length is 1.38 Å. In the seventh C site, C(7) is bonded in a distorted single-bond geometry to one C(6), one C(8), and one H(3) atom. The C(7)-C(8) bond length is 1.38 Å. The C(7)-H(3) bond length is 0.93 Å. In the eighth C site, C(8) is bonded in a trigonal planar geometry to one C(12), one C(7), and one C(9) atom. The C(8)-C(12) bond length is 1.50 Å. The C(8)-C(9) bond length is 1.39 Å. In the ninth C site, C(9) is bonded in a distorted single-bond geometry to one C(10), one C(8), and one H(4) atom. The C(9)-C(10) bond length is 1.38 Å. The C(9)-H(4) bond length is 0.93 Å. In the tenth C site, C(10) is bonded in a trigonal planar geometry to one C(11), one C(13), and one C(9) atom. The C(10)-C(11) bond length is 1.38 Å. The C(10)-C(13) bond length is 1.51 Å. In the eleventh C site, C(11) is bonded in a distorted single-bond geometry to one C(10), one C(6), and one H(5) atom. The C(11)-H(5) bond length is 0.93 Å. In the twelfth C site, C(12) is bonded in a distorted bent 120 degrees geometry to one C(8), one O(1), and one O(2) atom. The C(12)-O(1) bond length is 1.24 Å. The C(12)-O(2) bond length is 1.25 Å. In the thirteenth C site, C(13) is bonded in a distorted bent 120 degrees geometry to one C(10), one O(3), and one O(4) atom. The C(13)-O(3) bond length is 1.27 Å. The C(13)-O(4) bond length is 1.23 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Mn(1) and two equivalent C(2) atoms. In the second N site, N(2) is bonded in a trigonal planar geometry to one Mn(1) and two equivalent C(4) atoms. There are five inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(1) 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(7) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(9) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(11) atom. There are five inequivalent O sites. In the first O site, O(3) is bonded in a bent 120 degrees geometry to one Cu(2) and one C(13) atom. In the second O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Cu(1) and one C(13) atom. In the third O site, O(5) is bonded to one Mn(1), one Cu(2), and two equivalent Cu(1) atoms to form distorted corner-sharing OMnCu3 tetrahedra. In the fourth O site, O(1) is bonded in a single-bond geometry to one C(12) atom. In the fifth O site, O(2) is bonded in a single-bond geometry to one Cu(3) and one C(12) atom. Linkers: 7 [O]C(=O)c1cc(C([O])=O)cc(/C2=C3\C=C/C(=C(\c4cc(C([O])=O)cc(C([O])=O)c4)C4=N/C(=C(/c5cc(C([O])=O)cc(C([O])=O)c5)C5=CC=C([N]5)/C(c5cc(C([O])=O)cc(C([O])=O)c5)=C5/C=CC2=N5)C=C4)[N]3)c1. Metal clusters: 6 [C]1O[Cu]O[C]O[Cu]2O[Cu]2O1.[C]1O[Cu]O[C]O[Cu]2O[Cu]2O1.[Mn] ,12 O=[C]O[Cu]O[C]=O. The MOF has largest included sphere 17.29 A, density 0.97 g/cm3, surface area 3298.79 m2/g, accessible volume 0.64 cm3/g