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Title: Mononuclear and binuclear copper(II) bis(1,3-benzodioxole-5-carboxylate) adducts with bulky pyridines
Author: Soldevila-Sanmartín, Joan
Ayllón, J. A.
Calvet Pallàs, Maria Teresa
Font Bardia, Ma. Mercedes
Pons, Josefina
Keywords: Estructura cristal·lina (Sòlids)
Layer structure (Solids)
Issue Date: Apr-2017
Publisher: Elsevier Ltd
Abstract: Copper(II) bis(1,3-benzodioxole-5-carboxylate) adducts with bulky pyridines have been prepared from the reaction of copper(II) acetate with 1,3-benzodioxole-5-carboxylic acid (piperonylic acid, HPip) and an excess of pyridine derivatives (3-phenylpyridine, 3-Phpy, 4-phenylpyridine, 4-Phpy, or 4-benzylpyridine, 4-Bzpy). Using 3-Phpy or 4-Bzpy binuclear paddle wheel compounds ([Cu(μ-Pip)2(3-Phpy)]2 (1) and [Cu(μ-Pip)2(4-Bzpy)]2 (3), and mononuclear complexes [Cu(μ-Pip)2(3-Phpy)2(H2O)] (2) and {[Cu(Pip)2(4-Bzpy)2]}{[Cu(Pip)2(4-Bzpy)2](HPip)}·{4A}{4B} have been isolated. Mononuclear 2 can also be produced from 1 in presence of an excess of 3-Phpy, while low thermal treatment of 2 at 70 °C, in absence of solvent, reverts to the formation of 1. On the other hand, 4 presents a singular structure that contains two independent mononuclear units {4A} and {4B}. Working with 4-Phpy yields crystalline binuclear [Cu(μ-Pip)(Pip)(4-Phpy)2]2·4CH3OH (5). In this complex only half of the carboxylate ligands bridge copper atoms, being one of the rare examples of this flat core. Its crystal structure contains a significant fraction of volume filled with methanol that is partly lost simply by exposing the solid to air. However, this process is related to an irreversible structure collapse, showing that the intermolecular interactions after methanol removal are not enough to support a porous structure.
Note: Versió postprint del document publicat a:
It is part of: Polyhedron, 2017, vol. 126, p. 184-194
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ISSN: 0277-5387
Appears in Collections:Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada)

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