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Molecular structures of two compounds obtained in reactions of alumazene [DippNAlMe] 3 (1, Dipp = 2,6-i-Pr 2 C 6 H 3) with substituted quinolinols have been elucidated by the single-crystal X-ray diffraction analysis. Quinolin-8-ol (Hq) provides a dinuclear complex [(DippNH) 2 Al 2 Me 2 (q) 2 ] (2) with a central Al 2 O 2 ring and five-coordinate Al atoms. The compound 2. THF crystallizes in the orthorhombic Pbca space group. The molecular structure of a mononuclear complex [(DippNH)Al(Meq) 2 ] (3) obtained in the reaction of 1 with 2-methylquinolin-8-ol (HMeq) possesses a five-coordinate Al center. The structure was solved in a triclinic cell P−1. The dinuclear complex 2 can be considered as a model product of alcohol addition on the formal Al−N double bond, while the mononuclear complex 3 represents subsequent reaction of remaining Al−Me moiety with proton. Both complexes 2 and 3 are highly luminescent showing emission around 500 nm in solid state.