| Abstract: | The 18‐membered mixed‐donor macrocycle 6,7,8,9,10,11,12,13,20,21‐decahydro‐5H, 19H‐dibenzob,m]1,15,5,8,11]dioxatriazacyclooctadecin‐20‐ol ( L ), which contains N3O3 donor set, was synthesized. Also two nickel(II) complexes of L have been synthesized and characterized by X‐ray crystallography, FT‐IR, UV‐Vis absorption spectroscopy and elemental analysis. The structure of complexes shows an unexpected anion dependence. Reaction of Ni(ClO4)2·6H2O with L afforded Ni L ](ClO4)2·CH2Cl2 complex in which L uses all donor atoms and acts as a hexadentate ligand so forming a mononuclear nickel(II) complex in distorted octahedral geometry. Contrasting with this, when NiCl2·6H20 is used, the product complex {Ni L Cl}2(μ‐Cl)2] is dimeric and consists of two Ni L Cl units bridged by two chloride ions. The coordination geometry of each nickel atom is a distorted octahedral. In this complex L is exo‐coordinated via only three nitrogen atoms to a nickel ion, which is bound to two cis bridging chloride and one non‐bridging chloride too. Also complexing properties of L towards Ni(ClO4)2·6H2O and NiCl2·6H20 have been determined by UV‐Vis titration in methanol. The computer treatment of the data confirmed the 1:1 metal to ligand stoichiometry for two complexes in solution and gave reliable values for corresponding stability constants (logK = 3.00 ± 0.02 with Ni(ClO4)2·6H2O and logK = 3.29 ± 0.06 with NiCl2·6H20). |
