Journal of the Iranian Chemical Society

, Volume 7, Issue 3, pp 727–739 | Cite as

A proton transfer self-associated compound from benzene-1,2,4,5-tetracarboxylic acid and piperazine and its cobalt(II) complex: Syntheses, crystal structures and solution studies

  • H. Aghabozorg
  • F. Mahfoozi
  • M. A. Sharif
  • A. Shokrollahi
  • S. Derki
  • M. Shamsipur
  • H. R. Khavasi


Two compounds containing a proton transfer ion pair (pipzH2)(btcH2), 1, and its Co(II) complex, were synthesized and characterized using IR spectroscopy and single crystal X-ray diffraction method. The chemical formula is {(pipzH2)[Co(btc)(H2O)4].4H2O}n for Co(II) complex, 2, (pipz:piperazine, btcH4:benzene-1,2,4,5-tetracarboxylic acid). The space group and crystal system of both compounds are \(P\bar 1\) and triclinic. The proton transfer ion pair 1 was prepared by the reaction between piperazine and benzene-1,2,4,5-tetracarboxylic acid, and its Co(II) complex, 2, was synthesized by the reaction of 1 with cobalt(II) sulphate. The complex 2 is a polymeric substance with Co(II) atoms linked by two O atoms from one benzene-1,2,4,5- tetracarboxylate. In both crystal structures, a wide range of noncovalent interactions consisting of hydrogen bonding (types of OH ⃛O, N-H⃛O and C-H⃛O) and ion pairing interactions connecting the various components into a supramolecular structure. There are also C-H⃛O and C-H⃛π intermolecular interactions in compound 2 which take part in the stabilization of molecular packing. The protonation constants of pipz and btcH4, the equilibrium constants for the btcH4-pipz proton transfer system and the stoichiometry and stability of this system with Co2+ ion in aqueous solution were investigated by potentiometric pH titrations. The stoicheiometry of one of the most abundant complexed species in solution was found to be the same as that of the crystalline cobalt(II) complex.


Cobalt(II) complex Benzene-1,2,4,5-tetracarboxylic acid Piperazine Crystal structure Solution study Hydrogen bond 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. [1]
    M. Eddaoudi, D.B. Moler, H.L. Li, B.L. Chen, T.M. Reineke, M. O’Keeffe, O.M. Yaghi, Acc. Chem. Res. 34 (2001) 319.Google Scholar
  2. [2]
    B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629.Google Scholar
  3. [3]
    S. Leininger, B. Olenyuk, P.J. Stang, Chem. Rev. 100 (2000) 853.Google Scholar
  4. [4]
    L. Pan, H.M. Liu, X.G. Lei, X.Y. Huang, D.H. Olson, N.J. Turro, J. Li, Angew. Chem. Int. Ed. 42 (2003) 542.Google Scholar
  5. [5]
    M. Fugita, Y.J. Kwon, S. Washizu, K. Ogura, J. Am. Chem. Soc. 116 (1994) 1151.Google Scholar
  6. [6]
    W.B. Lin, Z.Y. Wang, L. Ma, J. Am. Chem. Soc. 121 (1999) 11249.Google Scholar
  7. [7]
    S. Noro, S. Kitagawa, M. Kondo, K. Seki, Angew. Chem. Int. Ed. 39 (2000) 2082.Google Scholar
  8. [8]
    H. Kou, S. Gao, J. Zhang, G. Wen, G. Su, R.K. Zheng, X.X. Zhang, J. Am. Chem. Soc. 123 (2001) 11809.Google Scholar
  9. [9]
    Y.J. Qi, Y.H. Wang, C.W. Hu, M.H. Cao, L. Mao, E.B. Wang, Inorg. Chem. 42 (2003) 8519.Google Scholar
  10. [10]
    Y.J. Qi, Y.H. Wang, H.L. Fan, M.H. Cao, L. Mao, C.W. Hu, E.B. Wang, N.H. Hu, H.Q. Jia, J. Mol. Struct. 694 (2004) 73.Google Scholar
  11. [11]
    L. Wang, E.B. Wang, Chem. Res. Chinese U. 20 (2004) 127.Google Scholar
  12. [12]
    G.B. Deacon, R.J. Phillips, Coord. Chem. Rev. 33 (1980) 227.Google Scholar
  13. [13]
    H. Aghabozorg, F. Manteghi, S. Sheshmani, J. Iran. Chem. Soc. 5 (2008) 184.CrossRefGoogle Scholar
  14. [14]
    H. Aghabozorg, M. Ghadermazi, S. Sheshmani, J. Attar Gharamaleki, Acta Cryst. E63 (2007) o2985.Google Scholar
  15. [15]
    H. Aghabozorg, M. Ghadermazi, J. Attar Gharamaleki, Acta Cryst. E62 (2006) o3174.Google Scholar
  16. [16]
    H. Aghabozorg, F. Manteghi, M. Ghadermazi, Acta Cryst. E64 (2008) o740.Google Scholar
  17. [17]
    G.M. Sheldrick, SHELXTL, Vol. 5.10, Structure Determination Software Suite, Bruker AXS, Madison.Google Scholar
  18. [18]
    A.C. Gonzalez-Baro’, E.E. Castellano, O.E. Piro, B.S. Parajo’n-Costa, Polyhedron 24 (2005) 49.Google Scholar
  19. [19]
    D.H. Williams, I. Fleming, Spectroscopic Methods in Organic Chemistry, 5th ed., McGraw-hill, London, 1995.Google Scholar
  20. [20]
    A. Shokrollahi, M. Ghaedi, H.R. Rajabi, M. Sadat, Niband, Spectrochim. Acta A 71 (2008) 655.Google Scholar
  21. [21]
    A. Moghimi, S. Sheshmani, A. Shokrollahi, M. Shamsipur, G. Kickelbik, H. Aghabozorg, Z. Anorg, Allg. Chem. 631 (2005) 160.Google Scholar
  22. [22]
    H. Aghabozorg, F. Ramezanipour, J. Soleimannejad, M.A. Sharif, A. Shokrollahi, M. Shamsipur, A. Moghimi, J. Attar Gharamaleki, V. Lippolis, A.J. Blake, Polish J. Chem. 82 (2008) 487.Google Scholar
  23. [23]
    A. Shokrollahi, M. Ghaedi, H. Ghaedi, J. Chin. Chem. Soc. 54 (2007) 933.Google Scholar
  24. [24]
    A. Shokrollahi, M. Ghaedi, H.R. Rajabi, Ann. Chim. 97 (2007) 823.Google Scholar
  25. [25]
    A. Shokrollahi, M. Ghaedi, M.S. Niband, H.R. Rajabi, J. Hazard. Mater. 151 (2008) 642.Google Scholar
  26. [26]
    A.E. Martell, R.J. Motekaitis, Determination and Use of Stability Constants, 2nd ed., VCH, New York, 1992.Google Scholar
  27. [27]
    D. Cremer, J.A. Pople, J. Am. Chem. Soc. 97 (1975) 1354.Google Scholar
  28. [28]
    F.D. Rochon, G. Massarweh, Inorg. Chim. Acta 314 (2001) 163.Google Scholar
  29. [29]
    S. Bhaskaran, S. Selvanayagan, D. Velmurugan, K. Ravikumar, N. Arumugan, R. Raghunathan, Anal. Sci. 22 (2006) x57.Google Scholar
  30. [30]
    G.R. Desiraju, T. Steiner, The Weak Hydrogen Bond in Structural Chemistry and Biology, Oxford: Oxford University Press, 1999, pp. 1–28.Google Scholar
  31. [31]
    Z.M. Wang, L.J. van de Burgt, G.R. Choppin, Inorg. Chim. Acta 293 (1999) 167.Google Scholar
  32. [32]
    H. Aghabozorg, F. Manteghi, M. Ghadermazi, M. Mirzaei, A.R. Salimi, A. Shokrollahi, S. Derki, H. Eshtiagh-Hosseini, J. Mol. Struct. 919 (2008) 381.Google Scholar

Copyright information

© Iranian Chemical Society 2010

Authors and Affiliations

  • H. Aghabozorg
    • 1
  • F. Mahfoozi
    • 2
  • M. A. Sharif
    • 3
  • A. Shokrollahi
    • 4
  • S. Derki
    • 4
  • M. Shamsipur
    • 5
  • H. R. Khavasi
    • 6
  1. 1.Faculty of ChemistryTarbiat Moallem UniversityTehranIran
  2. 2.Department of ChemistryIslamic Azad University, Neiriz fars BranchNeiriz farsIran
  3. 3.Department of ChemistryIslamic Azad University, Qom BranchQomIran
  4. 4.Department of ChemistryYasouj UniversityYasoujIran
  5. 5.Department of ChemistryRazi UniversityKermanshahIran
  6. 6.Department of ChemistryShahid Beheshti UniversityTehranIran

Personalised recommendations