Mn8C36H12(S2O9)3 crystallizes in the trigonal R-3c space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(5), and two equivalent O(4) atoms to form MnO5 square pyramids that share corners with two equivalent Mn(2)O6 octahedra,  a cornercorner with one Mn(1)O5 square pyramid, and  an edgeedge with one Mn(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 63-66°. The Mn(1)-O(1) bond length is 2.09 Å. The Mn(1)-O(2) bond length is 2.23 Å. The Mn(1)-O(5) bond length is 2.11 Å. There is one shorter (2.18 Å) and one longer (2.19 Å) Mn(1)-O(4) bond length. In the second Mn site, Mn(2) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form MnO6 octahedra that share corners with six equivalent Mn(1)O5 square pyramids and  a faceface with one Mn(2)O6 octahedra. All Mn(2)-O(2) bond lengths are 2.29 Å. All Mn(2)-O(3) bond lengths are 2.16 Å. There are six inequivalent C sites. In the first C site, C(6) is bonded in a distorted trigonal planar geometry to one C(1), one C(4), and one H(2) atom. The C(6)-C(1) bond length is 1.35 Å. The C(6)-C(4) bond length is 1.41 Å. The C(6)-H(2) bond length is 0.93 Å. In the second C site, C(1) is bonded in a trigonal planar geometry to one C(3), one C(6), and one S(1) atom. The C(1)-C(3) bond length is 1.48 Å. The C(1)-S(1) bond length is 1.71 Å. In the third C site, C(2) is bonded in a distorted bent 120 degrees geometry to one C(5), one O(1), and one O(5) atom. The C(2)-C(5) bond length is 1.50 Å. The C(2)-O(1) bond length is 1.25 Å. The C(2)-O(5) bond length is 1.24 Å. In the fourth C site, C(3) is bonded in a distorted bent 120 degrees geometry to one C(1), one O(3), and one O(4) atom. The C(3)-O(3) bond length is 1.23 Å. The C(3)-O(4) bond length is 1.27 Å. In the fifth C site, C(4) is bonded in a distorted trigonal planar geometry to one C(5), one C(6), and one H(1) atom. The C(4)-C(5) bond length is 1.37 Å. The C(4)-H(1) bond length is 0.93 Å. In the sixth C site, C(5) is bonded in a trigonal planar geometry to one C(2), one C(4), and one S(1) atom. The C(5)-S(1) bond length is 1.71 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(4) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(6) atom. S(1) is bonded in an L-shaped geometry to one C(1) and one C(5) atom. There are five inequivalent O sites. In the first O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Mn(1) and one C(3) atom. In the second O site, O(1) is bonded in a bent 120 degrees geometry to one Mn(1) and one C(2) atom. In the third O site, O(2) is bonded to two equivalent Mn(1) and two equivalent Mn(2) atoms to form edge-sharing OMn4 tetrahedra. In the fourth O site, O(3) is bonded in a bent 120 degrees geometry to one Mn(2) and one C(3) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one Mn(1) and one C(2) atom. Linkers: 12 [O]C(=O)c1ccc(C([O])=O)s1. Metal clusters: 2 [C]1O[Mn]23O[C]O[Mn@]45O[C]O[Mn@](O[C]O[Mn]2(O[C]O[Mn@]26O[C]O[Mn@](O1)(O[C]O2)O6)O[C]O[Mn@]12O[C]O[Mn@](O[C]O3)(O[C]O1)O2)(O[C]O4)O5. RCSR code: pcu. The MOF has largest included sphere 7.08 A, density 1.33 g/cm3, surface area 2937.78 m2/g, accessible volume 0.35 cm3/g