4-Pyrimidinyl nitronyl nitroxide (4PMNN) was synthesized and characterized, and four 4PMNN-metal(II) chloride complexes were investigated. Hexanuclear macrocyclic [CUCl2.(4PMNN)](6) shows intermolecular ferromagnetic interaction. MnCl2.(4PMNN) exhibits antiferromagnetic interaction. Mononuclear COCl2.(4PMNN)2 shows ferrimagnetic phase transition at ca. 3 K. NiCl2.(4PMNN)(2) are practically diamagnetic below 100 K.