Synchrotron charge-density studies in materials chemistry:: 16 K X-ray charge density of a new magnetic metal-organic framework material, [Mn2(C8H4O4)2(C3H7NO)2]

A new magnetic metal-organic framework material, [Mn-2(C8OH44)(2)(C3H7NO)(2)], has been synthesized. The structure consists of chains of carboxylate-bridged Mn atoms interconnected with acid linkers, giving much larger interchain than intrachain Mn...Mn distances. Magnetic susceptibility data fitted to a Curie-Weiss law give Theta=-5.7 K and a total magnetic moment of 5.96 mu(B). The heat capacity provides no evidence of magnetic ordering down to 2 K. The X-ray charge density was determined from multipole modeling of 16 (1) K single-crystal synchrotron-radiation data. The structural surroundings of the two unique Mn centers are different, but orbital population analysis reveals close to single electron occupation in all 3d orbitals of both Mn sites, in agreement with the magnetic susceptibility measurements. Bader topological analysis shows the presence of direct chemical Mn...Mn interactions only in two out of three intrachain contacts, which suggests a 'broken' chain. The topological measures and approximate energy densities at the metal-ligand bond critical points (rho, del(2)rho, G, V and H) indicate ionic interactions. Formal electron counting suggests mixed-valence Mn sites, but this hypothesis is not supported by the Bader atomic charges [q(Mn)=+2.035 and +2.031].