Two heteronuclear compounds (1 and 2) containing three ferric centers linked in facial-like mode with the magnetically silent hexacyanidocobaltate(III) anion were prepared and studied. The structural investigation revealed that both compounds are tetranuclear complexes with molecular formulas of [{Fe(L1)NC}(3)Co(CN)(3)]center dot 2CH(3) OH center dot 2.5CH(3)CN (1) and [{Fe(L2)NC}(3)Co(CN)(3)]center dot 2H(2)O center dot]CH3OH (2). The magnetic properties of both complexes are controlled by the molecular design of the corresponding pentadentate Schiff base anions L1(2-) and L2(2-). While compound 2 with a symmetric ligand prepared from salicylaldehyde shows high-spin state properties, compound 1 containing the asymmetric ligand with naphthalene units either is low-spin in its solvated form or shows a gradual but hysteretic spin crossover event when desolvated. The magnetic behavior was analyzed with respect to the Ising-like model and spin Hamiltonian, respectively, and the results were confronted with ab initio calculations. Additionally, the influence of structural features, lattice solvent molecules, the distribution of electronic terms, and active orbitals on the spin state properties of reported complexes is discussed.