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Abstract: The light green coloured complexes of general formula [ReVO(L)Cl(OH2)]Cl have been synthesised in good yields by reacting [ReVOCl3(AsPh3)2] with HL in dichloromethane in dinitrogen atmosphere. Here, L− is the deprotonated form of N,N-bis(2-pyridylmethyl)amine (HL1); N-(2-pyridylmethyl)-N′,N′-dimethylethylenediamine (HL2) and N-(2-pyridylmethyl)-N′,N′-diethylethylenediamine (HL3). Single crystal X-ray structure determination of [ReVO(L1)Cl(OH2)]Cl confirms the amido binding of ReO3+ species. In the solid state of [ReVO(L1)Cl(OH2)]Cl, the coordinated and counter chloride ions are engaged in Re–Cl…H–C(ring), Cl…H–C(ring) and Re–(OH2)…Cl hydrogen bonding and forming of a supramolecular network in the solid state. The subunit of the supramolecular network consists of one eight-membered and two nine-membered hydrogen bonded rings. The average diameters of eight-membered and nine-membered rings are ∼3.70 and ∼5.26Å, respectively. [Copyright &y& Elsevier]