The insight into the influence of the geometry of the coordination polyhedra and the ligand field on the magnetic properties of 1 -3 has also been evaluated using theoretical methods based on the state average complete active space self-consistent field (SA-CASSCF) calculations followed by SINGLE_ANISO analysis. The calculations were performed with ORCA 5.0 software and the computational details are described in the Experimental section. The respective molecular structures were derived from the experimental X-ray data and only the hydrogen atom positions were optimized. In the case of compound 3, there are two molecular units in the asymmetric unit with dysprosium atoms Dy1 and Dy2, herein labelled as 3a and 3b, respectively. Moreover, there is a potentially significant hydrogen bond of methanol molecules to acac anion of 3b. Previously, some of us and other authors pointed to the significance of the second coordination sphere in SMMs, therefore, the computations were also performed for the complex {[Dy(acac)3(bik-