HMn(CO)5 crystallizes in the trigonal R-3 space group. Mn(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form distorted edge-sharing MnO6 octahedra. The Mn(1)-O(2) bond length is 2.10 Å. The Mn(1)-O(5) bond length is 2.57 Å. There is one shorter (2.16 Å) and one longer (2.19 Å) Mn(1)-O(1) bond length. There is one shorter (2.08 Å) and one longer (2.10 Å) Mn(1)-O(3) bond length. There are five inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(2), one O(1), and one O(2) atom. The C(1)-C(2) bond length is 1.48 Å. The C(1)-O(1) bond length is 1.29 Å. The C(1)-O(2) bond length is 1.28 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(3), and one C(4) atom. The C(2)-C(3) bond length is 1.43 Å. The C(2)-C(4) bond length is 1.40 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(2), one C(4), and one O(3) atom. The C(3)-C(4) bond length is 1.40 Å. The C(3)-O(3) bond length is 1.35 Å. In the fourth C site, C(4) is bonded in a distorted trigonal planar geometry to one C(2), one C(3), and one H(1) atom. The C(4)-H(1) bond length is 1.09 Å. In the fifth C site, C(5) is bonded in a linear geometry to one O(4) and one O(5) atom. The C(5)-O(4) bond length is 1.17 Å. The C(5)-O(5) bond length is 1.18 Å. H(1) is bonded in a single-bond geometry to one C(4) atom. There are five inequivalent O sites. In the first O site, O(2) is bonded in a bent 120 degrees geometry to one Mn(1) and one C(1) atom. In the second O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Mn(1) and one C(3) atom. In the third O site, O(4) is bonded in a single-bond geometry to one C(5) atom. In the fourth O site, O(5) is bonded in a bent 120 degrees geometry to one Mn(1) and one C(5) atom. In the fifth O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Mn(1) and one C(1) atom. Linkers: 3 [O]C(=O)c1cc([O])c(C([O])=O)cc1[O]. Metal clusters: 6 [Mn]. The MOF has largest included sphere 7.32 A, density 1.39 g/cm3, surface area 3204.70 m2/g, accessible volume 0.40 cm3/g