Bond orders for intermolecular interactions in crystals: charge transfer, ionicity and the effect on intramolecular bonds

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  • Khidhir Alhameedi, University of Western Australia, University of Karbala
  • ,
  • Amir Karton, University of Western Australia
  • ,
  • Dylan Jayatilaka, University of Western Australia
  • ,
  • Sajesh P. Thomas

The question of whether intermolecular interactions in crystals originate from localized atom center dot center dot center dot atom interactions or as a result of holistic molecule center dot center dot center dot molecule close packing is a matter of continuing debate. In this context, the newly introduced Roby-Gould bond indices are reported for intermolecular 'sigma-hole' interactions, such as halogen bonding and chalcogen bonding, and compared with those for hydrogen bonds. A series of 97 crystal systems exhibiting these interaction motifs obtained from the Cambridge Structural Database (CSD) has been analysed. In contrast with conventional bond-order estimations, the new method separately estimates the ionic and covalent bond indices for atom center dot center dot center dot atom and molecule center dot center dot center dot molecule bond orders, which shed light on the nature of these interactions. A consistent trend in charge transfer from halogen/chalcogen bond-acceptor to bond-donor groups has been found in these intermolecular interaction regions via Hirshfeld atomic partitioning of the electron populations. These results, along with the 'conservation of bond orders' tested in the interaction regions, establish the significant role of localized atom center dot center dot center dot atom interactions in the formation of these intermolecular binding motifs.

Original languageEnglish
Pages (from-to)635-646
Number of pages12
Publication statusPublished - Sep 2018

    Research areas

  • intermolecular interactions, bond order, ionicity, hydrogen bonding, halogen bonding, crystal engineering, computational modelling, molecular crystals, CAMBRIDGE STRUCTURAL DATABASE, ATOM-ATOM BONDS, DENSITY ANALYSIS, HALOGEN BOND, CHALCOGEN, HYDROGEN, PERSPECTIVE, DEFINITION, MOLECULES, ENERGIES

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