The enrichment ratio of atomic contacts in crystals, an indicator derived from the Hirshfeld surface analysis

Abstract : The partitioning of space with Hirshfeld surfaces enables the analysis of fingerprint molecular interactions in crystalline environments. This study uses the decomposition of the crystal contact surface between pairs of interacting chemical species to derive an enrichment ratio. This quantity enables the analysis of the propensity of chemical species to form intermolecular interactions with themselves and other species. The enrichment ratio is obtained by comparing the actual contacts in the crystal with those computed as if all types of contacts had the same probability to form. The enrichments and contact tendencies were analyzed in several families of compounds, based on chemical composition and aromatic character. As expected, the polar contacts of the type H center dot center dot center dot N, H center dot center dot center dot O and H center dot center dot center dot S, which are generally hydrogen bonds, show enrichment values larger than unity. O center dot center dot center dot O and N center dot center dot center dot N contacts are impoverished while H center dot center dot center dot H interactions display enrichment ratios which are generally close to unity or slightly lower. In aromatic compounds, C center dot center dot center dot C contacts can display large enrichment ratios due to extensive pi center dot center dot center dot pi stacking in the crystal packings of heterocyclic compounds. C center dot center dot center dot C contacts are, however, less enriched in pure (C, H) hydrocarbons as pi center dot center dot center dot pi stacking is not so favourable from the electrostatic point of view compared with heterocycles. C center dot center dot center dot H contacts are favoured in (C, H) aromatics, but these interactions occur less in compounds containing O, N or S as some H atoms are then involved in hydrogen bonds. The study also highlights the fact that hydrogen is a prefered interaction partner for fluorine.
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Christian Jelsch, Krzysztof Ejsmont, Loic Huder. The enrichment ratio of atomic contacts in crystals, an indicator derived from the Hirshfeld surface analysis. IUCrJ = International Union of Crystallography journal, International Union of Crystallography 2014, 1 (2), pp.119-128. ⟨10.1107/S2052252514003327⟩. ⟨hal-01521319⟩

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