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Supramolecular self-assembly of new thiourea derivatives directed by intermolecular hydrogen bonds and weak interactions: crystal structures and Hirshfeld surface analysis

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Abstract

We synthesized and characterized a series of four closely related thiourea derivatives (1–4) obtained by reaction of 4-R-benzoyl chloride (R: H, Cl, CH3, and OCH3) with equimolar amount of potassium thiocyanate and dibenzylamine in dry acetone. The crystalline and molecular structures of the synthesized compounds 1–4 were examined to understand how the crystal packing of each compound altered when substituted by different functional groups at para position on the aromatic ring. Single-crystal X-ray diffraction analysis revealed that molecules of the prepared compounds assembled into supramolecular units connected via networks of similar intermolecular interactions. The packing arrangement of the compounds, however, was found to be different. We also conducted Hirshfeld surface analysis for all the synthesized compounds and followed the changes of different properties on these surfaces related to systematic variations of the substituent. Hirshfeld surface analysis and decomposed fingerprint plots showed that the structures were stabilized by H···H, H···S, O···H, N···H, C–H···π, and π···π intermolecular interactions, which contribute mostly to the packing of the species in the crystal. The two largest contributions to the packing of the molecules in the crystals were provided by H···H (51.6, 39.5, 54.4, and 51.4 %) and C–H···π (27.4, 27.1, 24.6, and 28.8 %) intermolecular interactions.

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Acknowledgements

This work was supported by the Mersin University Research Fund (Project No. 2016-AP4-1426). This academic work was supported linguistically by the Mersin Technology Transfer Office Academic Writing Center of Mersin University.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Arts and Science, Mersin University, 33343, Mersin, Turkey

    Ilkay Gumus, Ummuhan Solmaz, Birdal Arslan & Hakan Arslan

  2. Advanced Technology Research and Application Center, Mersin University, 33343, Mersin, Turkey

    Ebru Keskin

  3. Department of Chemistry, Faculty of Education, Mersin University, 33343, Mersin, Turkey

    Gun Binzet

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  1. Ilkay Gumus
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  2. Ummuhan Solmaz
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Correspondence to Ilkay Gumus.

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11164_2018_3596_MOESM1_ESM.docx

CCDC-1822580, 1822579, 1822576, and 1822577 contain the supplementary crystallographic data for compounds 1–4, respectively. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by e-mailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033 (DOCX 1682 kb)

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Gumus, I., Solmaz, U., Binzet, G. et al. Supramolecular self-assembly of new thiourea derivatives directed by intermolecular hydrogen bonds and weak interactions: crystal structures and Hirshfeld surface analysis. Res Chem Intermed 45, 169–198 (2019). https://doi.org/10.1007/s11164-018-3596-5

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