The crystal structures of two manganese complexes with the enaminoketone derivatives of 3-imidazoline nitroxide: MnL 2 COOMe (layered polymeric) and MnL 2 CF3 (DMF)2 (molecular) have been determined. The polymer structure of MnL 2 COOMe is the result of direct coordination of the nitroxyl O atoms of the neighboring bischelate fragments by the Mn atoms. This forms heterospin exchange clusters >N⋅-O–Mn(II)–O-N< with strong antiferromagnetic interactions between the odd electrons of the paramagnetic centers. The structure of MnL 2 CF3 (DMF)2 is characterized by ligand cis-coordination in the octahedral coordination polyhedron. Due to the molecular nature of the complex, the solid compound has only weak ferromagnetic intramolecular indirect exchange interactions. The charge states of atoms in coordination units was confirmed by X-ray photoelectron data.