Cu(NO<sub>3</sub>)<sub>2</sub>·3H<sub>2</sub>O-Mediated Synthesis of 4‘-(2-Pyridyl)-2,2‘:6‘,2‘ ‘-terpyridine (<b>L2</b>) from <i>N</i>-(2-Pyridylmethyl)pyridine-2-methylketimine (<b>L1</b>). A C−C Bond-Forming Reaction and the Structure of {[Cu(<b>L2</b>)(OH)(NO<sub>3</sub>)][Cu(<b>L2</b>)(NO<sub>3
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N-(2-Pyridylmethyl)pyridine-2-methylketimine (L1) was synthesized from equimolar quantities of (2-pyridyl)methylamine and 2-acetylpyridine. Methanolic solution of L1 reacted readily with Cu(NO3)2·3H2O in air, affording green solid of composition {[Cu(L2)(OH)(NO3)][Cu(L2)(NO3)2]}·2H2O, where L2 is 4‘-(2-pyridyl)-2,2‘:6‘,2‘ ‘-terpyridine. Oxidation of the active methylene group of L1 to an imide and then condensation with 2-acetylpyridine involving a C−C bond-forming reaction, mediated by a Cu2+ ion, are the essential steps involved in the conversion of L1 to L2. L2 is isolated by extrusion of Cu2+ with EDTA2-. The copper center in [Cu(L2)(OH)(NO3)] has a mer-N3O3 environment, and that in [Cu(L2)(NO3)2] has a distorted trigonal-bipyramidal geometry. Two H2O molecules held by C−H···O interactions are present in the predominantly hydrophobic channels of approximate cavity dimension 7.60 × 6.50 Å created by aromatic rings through π−π interactions.
