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Oxidovanadium(v) coordination compounds based on 1,5-bis(2-hydroxy-3-methoxybenzylidene)carbohydrazide: from discrete
Diana Dragancea1, Natalia Talmaci2, Sergiu Shova3
1"C. D. Nenitzescu" Institute of Organic and Supramolecular Chemistry of the Romanian Academy Splaiul Independentei 202B Bucharest Romania ddragancea@gmail.com.
None:
The reaction of NH4VO3 or VO(acac)2 with 1,5-bis(2-hydroxy-3-methoxybenzylidene)carbohydrazide (H4L) has led to the formation of new homometallic dinuclear and tetranuclear V(v) coordination compounds, namely (NH4)2[(VO2)2(L)]·2H2O (1) and [(VO2)(VO)(EtO)(HL)]2·2EtOH (2). The introduction of alkali metal cations (Na+ and Cs+) into the reaction resulted in the formation of the heterometallic hexanuclear [Na2(H2O)4][(VO2)4(HL)2]·16H2O compound 3 and the {[Cs2(H2O)2][(VO2)2(L)]} n coordination polymer 4. Their composition and structure were determined by IR, 1H and 13C NMR spectroscopy, and ESI-MS spectrometry. Single-crystal X-ray diffraction analysis of 1 reveals that the hexadentate L4- ligand coordinates to two V(v) atoms via an ONN and an ONO donor set, resulting in the formation of a dinuclear vanadium-based complex dianion, [(VO2)2(L)]2-. The charge is compensated by two NH4 + cations. In 2, two dinuclear vanadium-based [(VO2)(VO)(EtO)(HL)] entities, each containing the hexadentate Schiff base ligand HL3-, which utilizes a set of donor atoms in a manner analogous to that in 1, are bridged through oxido (V-O-V) bonds into a tetranuclear cluster. In compound 3, the hexadentate HL3- utilizes additional donor atoms to bind sodium cations to two [(VO2)2(HL)]- moieties. The [Na2(H2O)4]2+ cations are sandwiched by the oxygen atoms of the methoxy groups of the HL3- ligands and the oxide atoms of the VO2 core resulting in the formation of a hexanuclear cluster in 3. The structure of compound 4 is based on the mutually linked clusters containing monomeric [(VO2)2(L)]2- moieties and water-alkali chains {[Cs2(H2O)2]} n to form a 3D coordination framework.
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