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A flexible tetradentate ligand 1,6-bis(4′-pyridyl)-2,5-diazahexane (BPDH) reacts with tetrakis(acetonitrile)silver(I) tetrafluoroborate to form a novel two-dimensional network complex [Ag(BPDH)]BF4·CH3CN. The compound crystallizes in monoclinic, space group P21/n with a=14.121(2), b=7.0410(10), c=19.803(3) Å, β=94.700(10)°, V=1962.3(5) Å3 and Z=4. The solvate acetonitrile molecule and counter anions are incorporated in the channels formed between two adjacent sheets through CH⋯F, NH⋯F and NH⋯N hydrogen bonds. The spectroscopic properties of the complex as luminescent, thermogravimetric and electrospray mass spectrometry were also described.