Research on Chemical Intermediates

, Volume 45, Issue 2, pp 169–198 | Cite as

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

  • Ilkay GumusEmail author
  • Ummuhan Solmaz
  • Gun Binzet
  • Ebru Keskin
  • Birdal Arslan
  • Hakan Arslan


We synthesized and characterized a series of four closely related thiourea derivatives (14) 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 14 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.

Graphical abstract


Thiourea derivatives Hirshfeld surface analysis Crystal structure Supramolecular self-assembly Noncovalent interactions 



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.

Authors contribution

All authors contributed equally to this work.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflicts of interest.

Ethical approval

All ethical guidelines were adhered to.

Sample availability

Samples of the compounds are available from the author.

Supplementary material

11164_2018_3596_MOESM1_ESM.docx (1.6 mb)
CCDC-1822580, 1822579, 1822576, and 1822577 contain the supplementary crystallographic data for compounds 14, respectively. These data can be obtained free of charge via, or by e-mailing, 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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© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.Department of Chemistry, Faculty of Arts and ScienceMersin UniversityMersinTurkey
  2. 2.Advanced Technology Research and Application CenterMersin UniversityMersinTurkey
  3. 3.Department of Chemistry, Faculty of EducationMersin UniversityMersinTurkey

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