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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
Article
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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.

Graphical abstract

Keywords

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

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.

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 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)

References

  1. 1.
    R. Custelcean, Chem. Commun. 2008, 295 (2008)CrossRefGoogle Scholar
  2. 2.
    M. Obrzud, M. Rospenk, A. Koll, Phys. Chem. Chem. Phys. 16, 3209 (2017)CrossRefGoogle Scholar
  3. 3.
    U. Solmaz, I. Gumus, G. Binzet, O. Celik, G.K. Balci, A. Dogen, H. Arslan, J. Coord. Chem. 71(2), 200 (2018)CrossRefGoogle Scholar
  4. 4.
    A. Saeed, U. Florke, Acta Crystallogr. E 63, o3695 (2007)CrossRefGoogle Scholar
  5. 5.
    A. Saeed, M.F. Erben, U. Florke, J. Mol. Struct. 982, 91 (2010)CrossRefGoogle Scholar
  6. 6.
    A. Saeed, U. Florke, M.F. Erben, J. Sulfur Chem. 45, 318 (2014)CrossRefGoogle Scholar
  7. 7.
    M.G. Woldu, J. Dillen, Theor. Chem. Acc. 121, 71 (2008)CrossRefGoogle Scholar
  8. 8.
    A. Saeed, R. Qamar, T.A. Fattah, U. Florke, M.F. Erben, Res. Chem. Intermed. 43, 3053 (2017)CrossRefGoogle Scholar
  9. 9.
    A. Saeed, M.F. Erben, U. Shaheen, U. Florke, J. Mol. Struct. 1000, 49 (2011)CrossRefGoogle Scholar
  10. 10.
    J. Guang, A.J. Larson, J.C.G. Zhao, Adv. Synth. Catal. 357, 523 (2015)CrossRefGoogle Scholar
  11. 11.
    Z. Mao, A. Lin, Y. Shi, H. Mao, W. Li, Y. Cheng, C. Zhu, J. Org. Chem. 78, 10233 (2013)CrossRefGoogle Scholar
  12. 12.
    Q. Liu, B. Qiao, K.F. Chin, C.H. Tan, Z. Jiang, Adv. Synth. Catal. 356, 3777 (2014)CrossRefGoogle Scholar
  13. 13.
    R.D. Lopez, M.E. Lopez, A. Alcaine, P. Merino, R.P. Herrera, Org. Biomol. Chem. 12, 4503 (2014)CrossRefGoogle Scholar
  14. 14.
    W.M. Khairul, A.I. Daud, N.A.M. Hanifaah, S. Arshad, I.A. Razak, H.M. Zuki, M.F. Erben, J. Mol. Struct. 1139, 353 (2017)CrossRefGoogle Scholar
  15. 15.
    L. Qiao, J. Huang, W. Hu, Y. Zhang, J. Guo, W. Cao, K. Miao, B. Qin, J. Song, J. Mol. Struct. 1139, 149 (2017)CrossRefGoogle Scholar
  16. 16.
    A. Saeed, U. Florke, M.F. Erben, J. Sulfur Chem. 35, 318 (2014)CrossRefGoogle Scholar
  17. 17.
    R.S. Correa, K.M.D. Oliveira, F.G. Delolo, A. Alvarez, R. Mocelo, A.M. Plutin, M.R. Cominetti, E.E. Castellano, A.A. Batista, J. Inorg. Biochem. 150, 63 (2015)CrossRefGoogle Scholar
  18. 18.
    A.F. Elhusseiny, A. Eldissouky, A.M. Al-Hamza, H.H.A.M. Hassan, J. Mol. Struct. 1100, 530 (2015)CrossRefGoogle Scholar
  19. 19.
    N. Selvakumaran, A. Pratheepkumar, S.W. Ng, E.R.T. Tiekink, R. Karvembu, Inorg. Chim. Acta 404, 82 (2013)CrossRefGoogle Scholar
  20. 20.
    H. Mandal, D. Ray, Inorg. Chim. Acta 414, 127 (2014)CrossRefGoogle Scholar
  21. 21.
    V.B. Bregovic, N. Basaric, Coord. Chem. Rev. 295, 80 (2015)CrossRefGoogle Scholar
  22. 22.
    Y.M. Zhang, J.D. Qin, Q. Lin, T.B. Wei, J. Fluor. Chem. 38, 1222 (2006)CrossRefGoogle Scholar
  23. 23.
    D.H. Lee, H.Y. Lee, K.H. Lee, J. Hong, Chem. Commun. 32, 1188 (2001)CrossRefGoogle Scholar
  24. 24.
    J.L. Wu, Y.B. He, Z.Y. Zeng, L.H. Wei, L.Z. Meng, T.Z. Yang, Tetrahedron 60, 4309 (2004)CrossRefGoogle Scholar
  25. 25.
    L. Nie, Z. Li, J. Han, X. Zhang, R. Yang, W.X. Liu, F.Y. Wu, J.W. Xie, Y.F. Zhao, Y.B. Jiang, J. Org. Chem. 69, 6449 (2004)CrossRefGoogle Scholar
  26. 26.
    G. Binzet, I. Gumus, A. Dogen, U. Flörke, N. Kulcu, H. Arslan, J. Mol. Struct. 1161, 519 (2018)CrossRefGoogle Scholar
  27. 27.
    A. Okuniewski, J. Chojnacki, B. Becker, Acta Crystallogr. E. 68, 619 (2012)CrossRefGoogle Scholar
  28. 28.
    H. Perez, R.S. Correa, A.M. Plutin, B. O’Reilly, M.B. Andrade, Acta Crystallogr. C 68, 19 (2012)CrossRefGoogle Scholar
  29. 29.
    L.R. Gomes, L.M.N.B.F. Santos, J.A.P. Coutinho, B. Schroder, J.N. Low, Acta Crystallogr. E 66, 870 (2010)CrossRefGoogle Scholar
  30. 30.
    A. Saeed, U. Florke, M.F. Erben, J. Sulfur Chem. 35, 318 (2014)CrossRefGoogle Scholar
  31. 31.
    R.R. Cairo, A.M.P. Stevens, T.D. Oliveira, A.A. Batista, E.E. Castellano, J. Duque, D.B. Soria, A.C. Fantoni, R.S. Correa, M.F. Erben, Spectrochim. Acta A 176, 8 (2017)CrossRefGoogle Scholar
  32. 32.
    A. Saeed, M. Bolte, M.F. Erben, H. Pérez, CrystEngComm 17, 7551 (2015)CrossRefGoogle Scholar
  33. 33.
    A. Saeed, S. Ashraf, U. Florke, Z.Y.D. Espinoza, M.F. Erben, H. Pérez, J. Mol. Struct. 1111, 76 (2016)CrossRefGoogle Scholar
  34. 34.
    E.C. Aguilar, G.A. Echeverría, O.E. Piro, S.E. Ulic, J.L. Jios, M.E. Tuttolomondo, H. Pérez, Mol. Phys. 116, 399 (2018)CrossRefGoogle Scholar
  35. 35.
    O.V. Dolomanov, L.J. Bourhis, R.J. Gildea, J.A.K. Howard, H. Puschmann, J. Appl. Cryst. 42, 339 (2009)CrossRefGoogle Scholar
  36. 36.
    L. Palatinus, G. Chapuis, J. Appl. Cryst. 40, 786 (2007)CrossRefGoogle Scholar
  37. 37.
    L. Palatinus, A. van der Lee, J. Appl. Cryst. 41, 975 (2008)CrossRefGoogle Scholar
  38. 38.
    L. Palatinus, S.J. Prathapa, S. van Smaalen, J. Appl. Cryst. 45, 575 (2012)CrossRefGoogle Scholar
  39. 39.
    G.M. Sheldrick, Acta Cryst. C 71, 3 (2015)CrossRefGoogle Scholar
  40. 40.
    A. Linden, Spec. Acta Cryst. C 71, 9 (2015)CrossRefGoogle Scholar
  41. 41.
    M.J. Turner, J.J. McKinnon, S.K. Wolff, D.J. Grimwood, P.R. Spackman, D. Jayatilaka, M.A. Spackman, Crystal Explorer 17 (University of Western Australia, Crawley, 2017)Google Scholar
  42. 42.
    D.S. Mansuroglu, H. Arslan, U. Florke, N. Kulcu, J. Coord. Chem. 61, 3134 (2008)CrossRefGoogle Scholar
  43. 43.
    G. Avsar, H. Arslan, H.J. Haupt, N. Kulcu, Turk. J. Chem. 27, 281 (2003)Google Scholar
  44. 44.
    H. Arslan, U. Florke, N. Kulcu, Acta Chim. Slov. 51, 787 (2004)Google Scholar
  45. 45.
    M. Oki, Top. Stereochem. 14, 1 (1983)Google Scholar
  46. 46.
    M. Gemili, H. Sari, M. Ulger, E. Sahin, Y. Nural, Inorg. Chem. Acta. 463, 88 (2017)CrossRefGoogle Scholar
  47. 47.
    R. Quintanilla-Licea, J.F. Colunga-Valladares, A. Caballero-Quintero, C. Rodriguez-Padilla, R.T. Guerra, R. Gomez-Flores, N. Waksman, Molecules 7, 662 (2002)CrossRefGoogle Scholar
  48. 48.
    A. Rotondo, S. Barresi, M. Cusumano, E. Rotondo, Polyhedron 45, 23 (2012)CrossRefGoogle Scholar
  49. 49.
    A. Rotondo, S. Barresi, M. Cusumano, E. Rotondo, P. Donato, L. Mondello, Inorg. Chim. Acta 410, 1 (2014)CrossRefGoogle Scholar
  50. 50.
    K.R. Koch, Coord. Chem. Rev. 216–217, 473 (2001)CrossRefGoogle Scholar
  51. 51.
    C.K. Ozer, H. Arslan, D. VanDerveer, G. Binzet, J. Coord. Chem. 62, 266 (2009)CrossRefGoogle Scholar
  52. 52.
    I.V. Rubtsov, K. Kumar, R.M. Hochstrasser, Chem. Phys. Lett. 402, 439 (2005)CrossRefGoogle Scholar
  53. 53.
    H.M. Abosadiya, E.H. Anouar, S.A. Hasbullah, B.M. Yamin, Spectrochim. Acta A 144, 115 (2015)CrossRefGoogle Scholar
  54. 54.
    C.G. Overberger, H.A. Friedman, J. Polym. Sci. A 3, 3625 (1965)Google Scholar
  55. 55.
    L. Qiao, Y. Zhang, W. Hu, J. Guo, W. Cao, Z. Ding, Z. Guo, A. Fan, J. Song, J. Huang, J. Mol. Struct. 1141, 309 (2017)CrossRefGoogle Scholar
  56. 56.
    Z. Weiqun, L. Baolong, Z. Liming, D. Jiangang, Z. Yong, L. Lude, Y. Xujie, J. Mol. Struct. 690, 145 (2004)CrossRefGoogle Scholar
  57. 57.
    C.G. Overberger, H.A. Friedman, J. Polym. Sci. A 3, 3625 (1965)Google Scholar
  58. 58.
    A. Saeed, M.F. Erben, N. Abbas, U. Florke, J. Mol. Struct. 984, 240 (2010)CrossRefGoogle Scholar
  59. 59.
    C.N.R. Rao, R. Venkataraghavan, Spectrochim. Acta A 18, 541 (1962)CrossRefGoogle Scholar
  60. 60.
    A. Saeed, M.F. Erben, N. Abbas, U. Florke, J. Mol. Struct. 984, 240 (2010)CrossRefGoogle Scholar
  61. 61.
    M.S.M. Yusof, R.H. Jusoh, W.M. Khairul, B.M. Yamin, J. Mol. Struct. 975, 280 (2010)CrossRefGoogle Scholar
  62. 62.
    A. Saeed, M.F. Erben, M. Bolte, Spectrochim. Acta A 102, 408 (2013)CrossRefGoogle Scholar
  63. 63.
    M.F.M. Nasir, I.N. Hassan, W.R.W. Daud, B.M. Yamin, M.B. Kassim, Acta Crystallogr. E 67, o1987 (2011)CrossRefGoogle Scholar
  64. 64.
    M.F.M. Nasir, I.N. Hassan, B.M. Yamin, W.R.W. Daud, M.B. Kassim, Acta Crystallogr. E 67, o1742 (2011)CrossRefGoogle Scholar
  65. 65.
    N. Gunasekaran, R. Karvembu, S.W. Ngb, E.R.T. Tiekink, Acta Crystallogr. E 66, o2572 (2010)CrossRefGoogle Scholar
  66. 66.
    Y. Nural, M. Gemili, N. Seferoglu, E. Sahin, M. Ulger, H. Sari, J. Mol. Struct. 1160, 315 (2018)CrossRefGoogle Scholar
  67. 67.
    A. Saeed, A. Khurshid, M. Bolte, A.C. Fantoni, M.F. Erben, Spectrochim. Acta A 143, 59 (2015)CrossRefGoogle Scholar
  68. 68.
    H.M. Abosadiya, E.H. Anouar, S.A. Hasbullah, B.M. Yamin, Spectrochim. Acta A 92, 1386 (2015)Google Scholar
  69. 69.
    S. Subhankar, R. Lalit, J. Sumy, M.K. Manish, G. Somnath, R.D. Gautam, CrystEngComm 17, 1273 (2015)CrossRefGoogle Scholar
  70. 70.
    M.A. Spackman, D. Jayatilaka, CrystEngComm 11, 19 (2009)CrossRefGoogle Scholar
  71. 71.
    M.A. Spackman, J.J. McKinnon, CrystEngComm 4, 378 (2002)CrossRefGoogle Scholar
  72. 72.
    A.D. Santo, G.A. Echeverría, O.E. Piro, H. Pérez, A.B. Altabef, D.M. Gil, J. Mol. Struct. 1134, 492 (2017)CrossRefGoogle Scholar
  73. 73.
    J.J. McKinnon, M.A. Spackman, A.S. Mitchell, Acta Crystallogr. B 60, 627 (2004)CrossRefGoogle Scholar
  74. 74.
    A. Saeed, S. Ashraf, U. Florke, Z.Y.D. Espinoza, M.F. Erben, H. Perez, J. Mol. Struct. 1111, 76 (2016)CrossRefGoogle Scholar
  75. 75.
    S.K. Seth, D. Sarkar, A. Roy, T. Kar, CrystEngComm 13, 6728 (2011)CrossRefGoogle Scholar
  76. 76.
    I. Gumus, U. Solmaz, S. Gonca, H. Arslan, Eur. J. Chem. 8(4), 349 (2017)CrossRefGoogle Scholar
  77. 77.
    I. Gumus, S. Gonca, B. Arslan, E. Keskin, U. Solmaz, H. Arslan, Eur. J. Chem. 8(4), 410 (2017)CrossRefGoogle Scholar
  78. 78.
    I. Gumus, U. Solmaz, O. Celik, G. Binzet, G. Balcı, H. Arslan, Eur. J. Chem. 6(3), 237 (2015)CrossRefGoogle Scholar
  79. 79.
    A. Saeed, R. Qamar, T.A. Fattah, U. Flörke, M.F. Erben, Res. Chem. Intermed. 43(5), 3053 (2017)CrossRefGoogle Scholar

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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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