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ABSTRACT: The copper(I) complex [Cu(DPPEO)(L1)Cl]·CH3CN (1) (DPPEO=1,2-bis(diphenylphosphino)ethane monoxide; L1=5,7-dimethyl-2-chloronaphthyridine) was prepared by reacting L1 with CuCl in the presence of DPPE. The compound has been characterized by X-ray diffraction analysis. Compound 1 is a tri-coordinated mononuclear complex, which forms one-dimensional chain through intermolecular halogen-halogen bonds.