Mn2CH3S(NO)5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent N(2), one O(2), one O(3), and one O(4) atom to form MnN2O3 square pyramids that share corners with two equivalent Mn(2)N2O4 octahedra and corners with two equivalent S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. Both Mn(1)-N(2) bond lengths are 2.34 Å. The Mn(1)-O(2) bond length is 2.17 Å. The Mn(1)-O(3) bond length is 2.16 Å. The Mn(1)-O(4) bond length is 2.20 Å. In the second Mn site, Mn(2) is bonded to two equivalent N(1), two equivalent O(1), and two equivalent O(4) atoms to form MnN2O4 octahedra that share corners with two equivalent Mn(2)N2O4 octahedra, corners with two equivalent Mn(1)N2O3 square pyramids, and corners with two equivalent S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 74°. Both Mn(2)-N(1) bond lengths are 2.23 Å. Both Mn(2)-O(1) bond lengths are 2.21 Å. Both Mn(2)-O(4) bond lengths are 2.16 Å. C(1) is bonded in a trigonal planar geometry to one N(3) and two equivalent N(2) atoms. The C(1)-N(3) bond length is 1.36 Å. Both C(1)-N(2) bond lengths are 1.34 Å. There are three inequivalent N sites. In the first N site, N(3) is bonded in a trigonal planar geometry to one C(1) and two equivalent H(1) atoms. Both N(3)-H(1) bond lengths are 0.86 Å. In the second N site, N(1) is bonded in a distorted trigonal planar geometry to one Mn(2), one N(1), and one N(2) atom. The N(1)-N(1) bond length is 1.29 Å. The N(1)-N(2) bond length is 1.34 Å. In the third N site, N(2) is bonded in a 3-coordinate geometry to one Mn(1), one C(1), and one N(1) atom. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one N(3) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(4) atom. The H(2)-O(4) bond length is 0.84 Å. S(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form SO4 tetrahedra that share corners with two equivalent Mn(2)N2O4 octahedra and corners with two equivalent Mn(1)N2O3 square pyramids. The corner-sharing octahedral tilt angles are 56°. The S(1)-O(2) bond length is 1.47 Å. The S(1)-O(3) bond length is 1.47 Å. Both S(1)-O(1) bond lengths are 1.47 Å. There are four inequivalent O sites. In the first O site, O(4) is bonded in a distorted single-bond geometry to one Mn(1), two equivalent Mn(2), and one H(2) atom. In the second O site, O(1) is bonded in a bent 120 degrees geometry to one Mn(2) and one S(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one S(1) atom. In the fourth O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one S(1) atom. Linkers: 4 NC1=NN=N[N]1. Metal clusters: 8 [Mn]. The MOF has largest included sphere 4.00 A, density 1.98 g/cm3, surface area 2420.56 m2/g, accessible volume 0.17 cm3/g