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The synthesis, crystal structure, and magnetic properties of three new mononuclear complexes [Fe(R-LA)(L1)](BPh4), where R-LA2− is a doubly deprotonated pentadentate Schiff base ligand and L1 is a monodentate benzimidazole or furopyridine ligand, are reported. Ligand- and anion-driven changes in crystal structures and magnetic behavior were investigated in terms of the magnetic susceptibility measurements and theoretical calculations.