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Counterion effect on the formation of coordination polymer networks between AgNO₃ and L (2,2′-oxybis(ethane-2,1-diyl) diisonicotinate) Part 2

  • Sague, Jorge L. University of Geneva – Sciences II, Department of Inorganic, Analytical and Applied Chemistry, Geneva, Switzerland
  • Meuwly, Markus University of Basel, Department of Chemistry, Switzerland
  • Fromm, Katharina M. University of Fribourg, Department of Chemistry, Switzerland
    12.08.2008
Published in:
  • CrystEngComm. - 2008, vol. 10, p. 1542-1549
English Herein we report the synthesis and characterization by single crystal X-ray diffraction of three new silver(I) complexes {[Ag₂·L₂](NO₃)₂(H₂O)₄} (1), {[Ag₂·L₂](NO₃)₂} (2) and {[Ag₂·L₂](NO₃)₂} (3). Whereas compounds 2 and 3 are polymorphs, compound 1 crystallizes as the pseudo-polymorphic form of 2 and 3. These compounds were obtained from the reaction of silver nitrate with the flexible ligand 2,2′-oxybis(ethane-2,1-diyl) diisonicotinate (L). The main structural motifs for complexes 1–3 are zero-dimensional metallacycles, in which two silver(I) cations are coordinated by two ligands L and their counterions. As a result of its unpredictable coordinating ability, the nitrate anion coordinates the Ag(I) cation in a μ¹μ²-fashion in complex 1, in 2 it is coordinated in an asymmetrical μ²-mode, and in 3 the anion is strongly μ²-symmetrical coordinating. The coordination of the NO₃⁻ counterions to the metal cation affects the overall supramolecular interactions in the crystalline state of the complexes (e.g. Ag(I)⋯Ag(I), π⋯π, hydrogen bonds and C–H⋯π interactions). These interactions determine the physical properties of these compounds. On heating, the crystals of compound 3 are irreversibly transformed into compound 2. The conversion is supported by the change in the coordination mode of the nitrate counterion toward the Ag(I) cation. The solubility dependence of AgNO₃ in the different organic solvents used for the reactions may determine the structural diversity in the supramolecular architecture for these complexes.
Faculty
Faculté des sciences et de médecine
Department
Département de Chimie
Language
  • English
Classification
Chemistry
License
License undefined
Identifiers
Persistent URL
https://folia.unifr.ch/unifr/documents/301078
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