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The employment of the new Schiff base ligand 2-[(4-chloro-2-hydroxybenzylideneamino)methyl]phenol (H2 L) bearing O2N donors for the preparation of a novel Co6 cluster is reported. The hexanuclear cobalt complex, namely, di-μ2-acetatotetrakis{μ2-2-[(4-chloro-2-oxidobenzylideneamino)methyl]phenolato}tetra-μ3-methanolato-tetracobalt(II)dicobalt(III), [CoII 4CoIII 2(C14H10ClNO2)4(CH3COO)2(CH3O)4], was obtained using Co(CH3COO)2·4H2O and H2 L as starting materials in MeOH under solvothermal conditions. The six metal ions are linked together by the μ3-O atoms of four deprotonated MeOH molecules, two CH3COO− units and six phenolate O atoms of four L 2− ligands to form a defect disk-shaped topology. DC magnetic susceptibility investigations revealed the existence of antiferromagnetic interactions in the Co6 cluster.