Skip to main content
SpringerLink
Log in

Remarkably strong polarization of amidine fragment in the crystals of 1-imino-1H-isoindol-3-amine

  • Original Research
  • Published:
Structural Chemistry Aims and scope Submit manuscript

Abstract

Results of the X-ray diffraction studies of 1-imino-1H-isoindol-3-amine and its derivatives reveal unusual distribution of bond lengths within the NH2–C=N amidine fragment in the considered crystals. In the crystal phase, single C–N bond is shorter or at most has the same length as double C=N bond, while in isolated molecules both these bonds have expected lengths, according to the calculations by MP2/6-311G(d,p) and MP2/cc-pvtz methods. It is demonstrated that so unusually strong polarization of the amidine fragment is induced by polar environment in solid state. This effect stabilizes the amino-imino tautomer of 1-imino-1H-isoindol-3-amine, which becomes more stable than the diimino tautomer possessing the lowest energy in the gas phase.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1
Scheme 2
Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Fernando-Lazaro F, Torres T, Hauschel B, Hanack M (1998) Chem Rev 98:536

    Google Scholar 

  2. Radtke V, Erk P, Sens B (2002) In: Smith H (ed) Isoindoline pigments, in high performance pigments. Wiley, Weinheim

    Google Scholar 

  3. Hirohashi R, Sakamoto K, Ohno-Okumura E (2004) Phthalocyanines as functional dyes. ICP, Tokyo

    Google Scholar 

  4. Grant EB, Guiadeen D, Singer M, Argentieri D, Hlasta DJ, Wachter M (2001) Bioorg Med Chem Lett 11:2817

    Article  CAS  Google Scholar 

  5. Butner L, Huang Y, Tse E, Hall IH (1996) Biomed Pharmacother 50:290

    Article  CAS  Google Scholar 

  6. Callejon Mochnon M, Munoz Leyva JA (1986) Microchem J 34:83

    Article  Google Scholar 

  7. Hordienko OV, Biitseva AV, Kornilov MY, Brosse N, Hocquet A, Jamart-Gregoire B, Shishkin OV, Zubatyuk RI (2006) Eur J Org Chem 12:2833

    Article  Google Scholar 

  8. Hordienko OV, Rudenko IV, Biitseva AV, Turov AV, Arrault A, Brosse N, Fabre O, Jamart-Gregoire B, Zubatyuk RI, Shishkin OV (2009) Tetrahedron 65:6218

    Article  Google Scholar 

  9. Lyubimtsev AV, Baranski A, Islyaikin MK, Smirnov RP (1997) Chem Heterocycl Compd 27:435

    Google Scholar 

  10. Acker A, Hofman H-J, Cimiraglia R (1994) J Mol Struct (THEOCHEM) 315:43

    Article  Google Scholar 

  11. Zhang Z-Q, Njus JM, Sandman DJ, Guo C, Foxman BM, Erk P, Van Gelder R (2004) Chem Commun 886

  12. Elguero J, Marzin C, Katritzky AR, Linda P (1976) In: Katritzky AR, Boulton AJ (eds) Advances in Heterocyclic Chemistry, Suppl. 1, The Tautomerism of Heterocycles. Academic Press, New York

  13. Pawlowski G, Hanack M (1980) Synthesis 4:287

    Article  Google Scholar 

  14. Spiessens LI, Arteunis MJO (1988) Bull Soc Chim Belg 97:431

    Article  CAS  Google Scholar 

  15. Negrebetskii VV, Balitskaya OV, Kornilov MY (1983) Russ J Gen Chem 53:2573

    CAS  Google Scholar 

  16. Friedrichsen W, Traulsen T, Elguero J, Katritzky AR (2000) Tautomerism of heterocycles: five-membered rings with one heteroatom; advances in heterocyclic chemistry, vol 76. Academic Press, San Diego

    Google Scholar 

  17. Zhang Z-Q, Uth S, Sandman DJ, Foxman BM (2004) J Phys Org Chem 17:769

    Article  CAS  Google Scholar 

  18. Biitseva AV, Hordiyenko OV, Sukach VA, Vovk MV, Pichugin KA, Konovalova IS, Shishkin OV (2008) Monatsh Chem 139:939

    Article  CAS  Google Scholar 

  19. Shishkin OV, Kudrik EV, Islyaikin MK, Lyubimtsev AV, Siling SA (1998) Russ Chem Bull 47:327

    Article  CAS  Google Scholar 

  20. Shishkin OV, Gorb L, Leszczynski J (2000) J Phys Chem A 104:5357

    CAS  Google Scholar 

  21. Shishkin OV, Gorb L, Leszczynski J (2000) Int J Mol Sci 1:17

    Article  CAS  Google Scholar 

  22. Sukhanov OS, Shishkin OV, Gorb L, Leszczynski J (2008) Struct Chem 19:171

    Article  CAS  Google Scholar 

  23. Furmanchuk A, Shishkin OV, Isayev O, Gorb L, Leszczynski J (2010) Phys Chem Chem Phys 12:9945

    Article  CAS  Google Scholar 

  24. Gordienko OV, Negrebetskii VV, Ivanchenko VI, Kornilov MY (1989) Russ J Gen Chem 59:2771

    CAS  Google Scholar 

  25. Kornilov MY, Makovetsky VP (1974) Ukr Khim Zh 40:1175

    Google Scholar 

  26. Sheldrick GM (2008) Acta Crystallogr Sect A 64:112

    Article  CAS  Google Scholar 

  27. Møller C, Plesset MS (1934) Phys Rev 46:618

    Article  Google Scholar 

  28. Kendall RA, Dunning TH Jr, Harrison RJ (1992) J Chem Phys 96:6796

    Article  CAS  Google Scholar 

  29. McLean AD, Chandler GS (1980) J Chem Phys 72:5639

    Article  CAS  Google Scholar 

  30. Tomasi J, Mennucci B, Cammi R (2005) Chem Rev 105:2999

    Article  CAS  Google Scholar 

  31. Valiev M, Bylaska EJ, Govind N, Kowalski K, Straatsma TP, Van Dam HJJ, Wang D, Nieplocha J, Apra E, Windus TL, de Jong WA (2010) Comp Phys Commun 181:1477

    Article  CAS  Google Scholar 

  32. Neese F (2010) ORCA 2.8.0. Universitaet Bonn, Germany

    Google Scholar 

  33. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, revision A.01. Gaussian, Inc., Wallingford

    Google Scholar 

  34. Burgi H-B, Dunitz JD (1994) Structure correlation, vol 2. VCH, Weinheim

    Book  Google Scholar 

  35. Shishkin OV, Leszczynski J (1999) Chem Phys Lett 302:262

    Article  CAS  Google Scholar 

  36. Shishkin OV, Gorb L, Leszczynski J (2009) Struct Chem 20:743

    Article  CAS  Google Scholar 

  37. Biitseva AV, Rudenko IV, Hordiyenko OV, Jamart-Grégoire B, Arrault A (2012) Eur J Org Chem 2012:4387

    Article  CAS  Google Scholar 

  38. Elvidge JA, Barot NR (1977) In: Patai S (ed), The chemistry of functional groups part 2. imidines and diamidides (1,3,5-triazapentadienes). Wiley, London

Download references

Author information

Authors and Affiliations

  1. Division of Functional Materials Chemistry, SSI “Institute for Single Crystals”, National Academy of Science of Ukraine, 60 Lenina ave, Kharkiv, 61001, Ukraine

    Oleg V. Shishkin, Irina S. Konovalova, Roman I. Zubatyuk, Gennady V. Palamarchuk & Svitlana V. Shishkina

  2. Department of Inorganic Chemistry, V. N. Karazin National University, 4 Svobody sq, Kharkiv, 61077, Ukraine

    Oleg V. Shishkin

  3. Department of Organic Chemistry, National Taras Shevchenko University of Kyiv, 64 Volodymyrska str, Kyiv, 01601, Ukraine

    Angelina V. Biitseva, Igor V. Rudenko, Volodymyr A. Tkachuk, Mikhail Yu. Kornilov & Olga V. Hordiyenko

  4. Interdisciplinary Center for Nanotoxicity, Department of Chemistry and Biochemistry Jackson State University, P.O. Box 17910, 1325 Lynch Street, Jackson, MS, 39217, USA

    Jerzy Leszczynski

Authors
  1. Oleg V. Shishkin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Irina S. Konovalova
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Roman I. Zubatyuk
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Gennady V. Palamarchuk
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Svitlana V. Shishkina
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Angelina V. Biitseva
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Igor V. Rudenko
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Volodymyr A. Tkachuk
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Mikhail Yu. Kornilov
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Olga V. Hordiyenko
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Jerzy Leszczynski
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Oleg V. Shishkin.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Shishkin, O.V., Konovalova, I.S., Zubatyuk, R.I. et al. Remarkably strong polarization of amidine fragment in the crystals of 1-imino-1H-isoindol-3-amine. Struct Chem 24, 1089–1097 (2013). https://doi.org/10.1007/s11224-012-0131-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11224-012-0131-y

Keywords

Search

Navigation