Mononuclear and binuclear copper(II) bis(1,3-benzodioxole-5-carboxylate) adducts with bulky pyridines

Joan Soldevila-Sanmartín, José A. Ayllón*, Teresa Calvet, Merce Font-Bardia, Josefina Pons*

*Corresponding author for this work

Research output: Contribution to journalArticleResearchpeer-review

10 Citations (Scopus)

Abstract

© 2017 Elsevier Ltd 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.
Original languageEnglish
Pages (from-to)184-194
JournalPolyhedron
Volume126
DOIs
Publication statusPublished - 18 Apr 2017

Keywords

  • Binuclear Cu(II) complexes
  • Mononuclear Cu(II) complexes
  • Piperonylic acid
  • Pyridines
  • Supramolecular networks

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