AbstractThree high‐quality single‐crystal X‐ray diffraction data sets have been measured under very different conditions on a structurally simple, but magnetically complex, coordination polymer, [Mn(HCOO)2(H2O)2]∞(1). The first data set is a conventional 100(2) K MoKαdata set, the second is a very high resolution 100(2) K data set measured on a second‐generation synchrotron source, while the third data set was measured with a tiny crystal on a high brilliance third‐generation synchrotron source at 16(2) K. Furthermore, the magnetic susceptibility (χ) and the heat capacity (Cp) have been measured from 2 to 300 K on pressed powder. The charge density of1was determined from multipole modeling of the experimental structure factors, and overall there is good agreement between the densities obtained separately from the three data sets. When considering the fine density features, the two 100 K data sets agree well with each other, but show small differences to the 16 K data set. Comparison with ab initio theory suggests that the 16 K APS data set provides the most accurate density. Topological analysis of the metal–ligand bonding, experimental 3d orbital populations on the Mn atoms, and Bader atomic charges indicate quite ionic, high‐spin metal atoms. This picture is supported by the effective moment estimated from the magnetization measurements (5.840(2) μB), but it is at variance with earlier spin density measurements from polarized neutron diffraction. The magnetic ordering originates from superexchange involving covalent interactions with the ligands, and non‐ionic effects are observed in the static deformation density maps as well as in plots of the valence shell charge concentrations. Overall, the present study provides a benchmark charge density that can be used in comparison with future metal formate dihydrate charge densities.