This study is designed to identify relationships between structure and magnetic properties characteristic of coordination polymers (CPs), specifically in the model system {[Cu(HCOO)3]H2N(CH3)2}n. By determining the magnetic structure of two related CPs, in which a single magnetic pathway was systematically modified by substituting an HCOO- linker with topologically equivalent pyrimidine and NO3- ligands, respectively, we aim to address factors that tune the strength and nature of magnetic super-exchange. Moreover, the orientation of the magnetic moments and crystal-field anisotropy produced by the Jahn-Teller (JT) effect can be investigated. To achieve this goal essential information retrieved from neutron powder diffraction data measured as a function of temperature will be compared with the results of experimental charge density analysis, magnetic susceptibility, and magnetometry.