Lack of Cooperativity in the Triangular X3Halogen-Bonded Synthon?

Justyna Dominikowska*, Agnieszka J. Rybarczyk-Pirek, Célia Fonseca Guerra

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review


We have investigated 44 crystal structures, found in the Cambridge Structural Database, containing the X3 synthon (where X = Cl, Br, I) in order to verify whether three type II halogen-halogen contacts forming the synthon exhibit cooperativity. A hypothesis that this triangular halogen-bonded motif is stabilized by cooperative effects is postulated on the basis of structural data. However, theoretical investigations of simplified model systems in which the X3 motif is present demonstrate that weak synergy occurs only in the case of the I3 motif. In the present paper we computationally investigate crystal structures in which the X3 synthon is present, including halomesitylene structures, that are usually described as being additionally stabilized by a synergic interaction. Our computations find no cooperativity for halomesitylene trimers containing the X3 motif. Only in the case of two other structures containing the I3 synthon a very weak or weak synergy, i.e. the cooperative effect being stronger than -0.40 kcal mol-1, is found. The crystal structure of iodoform has the most pronounced cooperativity of all investigated systems, amounting to about 10% of the total interaction energy.

Original languageEnglish
Pages (from-to)597-607
Number of pages11
JournalCrystal Growth and Design
Issue number1
Early online date16 Dec 2020
Publication statusPublished - 6 Jan 2021

Bibliographical note

Funding Information:
The research was supported within the Project HPC-EUROPA3 (INFRAIA-2016-1-730897), with the support of the EC Research Innovation Action under the H2020 Programme (contract ID HPC17QP0HF, J.D.), by the National Science Centre of Poland (OPUS grant no. 2015/19/B/ST4/01773; A.J.R.-P.), and by The Netherlands Organization of Scientific Research (NWO-CW, NWO-EW; C.F.G.). Calculations were carried out using the computer resources and technical support provided by the SARA centre and by the Wrocław Centre for Networking and Supercomputing (grant no. 118). Access to HPC machines and licensed software is gratefully acknowledged by J.D.

Publisher Copyright:
© 2020 American Chemical Society.

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