Structural Chemistry

, 22:1365 | Cite as

Syntheses, crystal, molecular structures, and solution studies of Cu(II), Co(II), and Zn(II) coordination compounds containing pyridine-2,6-dicarboxylic acid and 1,4-pyrazine-2,3-dicarboxylic acid: comparative computational studies of Cu(II) and Zn(II) complexes

  • M. Mirzaei
  • H. Eshtiagh-Hosseini
  • N. Alfi
  • H. Aghabozorg
  • J. Attar Gharamaleki
  • S. A. Beyramabadi
  • H. R. Khavasi
  • A. R. Salimi
  • A. Shokrollahi
  • R. Aghaei
  • E. Karami
Original Research


Three new coordination compounds of Cu(II), Co(II), and Zn(II) based on different dicarboxylic acids formulated as (AcrH)[Cu(pydc)(pydcH)]·5H2O (1) (2a-4mpyH)2[M(pyzdc)2(H2O)2]·6H2O; M = Co(II) (2) and Zn(II) (3) have been synthesized and structurally characterized by elemental analyses, IR spectroscopy, and single crystal X-ray diffraction (where pydcH2 = pyridine-2,6-dicarboxylic acid; Acr = acridine; 2a-4mpy = 2-amino-4-methyl pyridine; pyzdcH2 = 1,4-pyrazin-2,3-dicarboxylic acid). In all cases, the metal centers have distorted octahedral coordination geometries. Through hydrogen bonding (such as O–H···O and N–H···O) and/or slipped or offset π–π stacking interactions, 3D supramolecular networks are constructed in these complexes. In the crystalline network, O–H···O hydrogen bonding create (H2O) n water clusters, so the hydrogen bond interactions play an important role in sustaining of the supramolecular solid-state architectures in compounds 13. The species in the solution media were studied by potentiometric method. The protonation constants of 2a-4mpy, 2-apy = 2-aminopyridine, pydc and pyzdc in aqueous solution, pydc and Acr in a 50% dioxane–50% water (v/v) solvent, as well as the equilibrium constants for three proton-transfer systems, pyzdc-2a-4mpy, pydc-2-apy, and pydc-Acr were calculated using potentiometrical method. The stoichiometry and stability of complexation during the first proton-transfer system with Cu2+, Co2+, and Zn2+ ions and also the second proton-transfer system with Fe3+ and Cr3+ ions in aqueous solution were investigated by potentiometric pH titration method, from point of comparison view of their behaviors in the solution state. The stoichiometry and stability of complexation of third system with Cu2+ and Zn2+, metal ions in 50% dioxane–50% water (v/v) solvent were also investigated by the cited method. The stoichiometry of the most complex species in solution were compared with corresponding crystalline metal ion complexes. Furthermore, DFT calculations have been carried out on the Cu(II) and Zn(II) complexes in the presence of pydcH2 and pyzdcH2 in order to better understanding of their molecular orbital structures of HOMO and LUMO.


Pyridine-2,6-dicarboxylic acid 1,4-Pyrazine-2,3-dicarboxylic acid Acridine Coordination compound Crystal structures Solution studies DFT 



The authors express their appreciation to the Ferdowsi University of Mashhad for financial support of this research paper (Grant No. P/18 and P/355). We also thank to Chemical Engineering Research Center for providing the opportunity to conduct the TG analyses.

Supplementary material

11224_2011_9829_MOESM1_ESM.doc (5.1 mb)
Supplementary material 1 (DOC 5226 kb)


  1. 1.
    Wang CJ, Wang YY, Liu JQ, Wang H, Shi QZ, Peng SM (2009) Inorg Chim Acta 362:543CrossRefGoogle Scholar
  2. 2.
    Çolak AT, Yeşilel OZ, Hökelek T, Şahin E (2008) Struct Chem 19:285 and Refs. [6–29] thereinGoogle Scholar
  3. 3.
    Chakraborty J, Shaikh N, Mayer-Figge H, Sheldrick WS, Vojtíšek P, Banerjee P (2007) Struct Chem 18:157CrossRefGoogle Scholar
  4. 4.
    Uçar I, Bulut I, Bulut A, Karadag A (2009) Struct Chem 20:825 and Refs. [8, 10, 14, 16, 17, 19, 20, 21] thereinGoogle Scholar
  5. 5.
    Dale SH, Elsegood MRJ, Coombs AEL (2004) Cryst Eng Commun 59:328Google Scholar
  6. 6.
    Eddaoudi M, Moler DB, Li H, Chen B, Reineke TM, O’keeffe M, Yaghi OM (2001) Acc Chem Res 34:319CrossRefGoogle Scholar
  7. 7.
    Shi Q, Zhang S, Wang Q, Ma H, Yang G, Sun WH (2007) J Mol Struct 837:185CrossRefGoogle Scholar
  8. 8.
    Moghimi A, Moosavi SM, Kordestani D, Maddah B, Shamsipur M, Aghabozorg H, Ramezanipour F, Kickelbick G (2007) J Mol Struct 828:38CrossRefGoogle Scholar
  9. 9.
    Vaidhyanathan R, Natarajan S, Rao CNR (2002) J Mol Struct 608:123CrossRefGoogle Scholar
  10. 10.
    Devereux M, McCann M, Leon V, McKee V, Ball RJ (2002) Polyhedron 21:1063CrossRefGoogle Scholar
  11. 11.
    Ene DC, Tuna F, Fabelo O, Ruiz-Pérez C, Madalan MA, Roesky WH, Andruh M (2008) Polyhedron 27:574CrossRefGoogle Scholar
  12. 12.
    Janiak C (2000) J Chem Soc Dalton Trans 3885Google Scholar
  13. 13.
    Beatty AM (2003) Coord Chem Rev 246:131CrossRefGoogle Scholar
  14. 14.
    Braga D, Maini L, Paganelli F, Tagliavini E, Casolari S, Grepioni F (2001) J Organomet Chem 609Google Scholar
  15. 15.
    Eppel S, Bernstein J (2008) Acta Cryst B 64:50CrossRefGoogle Scholar
  16. 16.
    Eshtiagh-Hosseini H, Yousefi Z, Mirzaei M (2009) Acta Cryst E65:o2816Google Scholar
  17. 17.
    Eshtiagh-Hosseini H, Yousefi Z, Mirzaei M, Chen YG, Shokrollahi A, Aghaei R (2010) J Mol Struct 973:1CrossRefGoogle Scholar
  18. 18.
    Eshtiagh-Hosseini H, Aghabozorg H, Mirzaei M, Amini MM, Chen YG, Shokrollahi A, Aghaei R (2010) J Mol Struct 973:180CrossRefGoogle Scholar
  19. 19.
    Eshtiagh-Hosseini H, Hassanpoor A, Alfi N, Mirzaei M, Fromm KM, Shokrollahi A, Gschwind F, Karami E (2010) J Coord Chem 63:3175CrossRefGoogle Scholar
  20. 20.
    Eshtiagh-Hosseini H, Yousefi Z, Shafiee M, Mirzaei M (2010) J Coord Chem 63:3187CrossRefGoogle Scholar
  21. 21.
    Eshtiagh-Hosseini H, Necas M, Alfi N, Mirzaei M (2010) Acta Cryst E 66:m1320CrossRefGoogle Scholar
  22. 22.
    Eshtiagh-Hosseini H, Alfi N, Mirzaei M, Marek N (2010) Acta Cryst E66:o2810Google Scholar
  23. 23.
    Eshtiagh-Hosseini H, Aghabozorg H, Mirzaei M (2010) Acta Cryst E66:m882Google Scholar
  24. 24.
    Eshtiagh-Hosseini H, Gschwind F, Alfi N, Mirzaei M (2010) Acta Cryst E66:m826Google Scholar
  25. 25.
    Eshtiagh-Hosseini H, Hassanpoor A, Mirzaei M, Salimi AR (2010) Acta Cryst E66:o2996Google Scholar
  26. 26.
    Eshtiagh-Hosseini H, Hassanpoor A, Canadillas-Delgado L, Mirzaei M (2010) Acta Cryst E66:o1368Google Scholar
  27. 27.
    Eshtiagh-Hosseini H, Hassanpoor A, Mirzaei M, Szymanska-Buzar T, Kochel A (2011) Acta Cryst E67:m455Google Scholar
  28. 28.
    Eshtiagh-Hosseini H, Mahjoobizadeh M, Mirzaei M (2010) Acta Cryst E66:o2210Google Scholar
  29. 29.
    Eshtiagh-Hosseini H, Mahjoobizadeh M, Mirzaei M, Fromm KM, Crochet A (2010) Eur J Chem 1:179CrossRefGoogle Scholar
  30. 30.
    Aghabozorg H, Manteghi F, Sheshmani S (2008) J Iran Chem Soc 5:184Google Scholar
  31. 31.
    Mirzaei M, Aghabozorg H, Eshtiagh-Hosseini H (2011) J Iran Chem Soc (in press)Google Scholar
  32. 32.
    Tabatabaee M, Aghabozorg H, Attar Gharamaleki J, Sharif AM (2009) Acta Cryst E 65:m473CrossRefGoogle Scholar
  33. 33.
    Aghabozorg H, Sadrkhanlou E, Soleimannejad J, Adams H (2007) Acta Cryst E 63:m1760CrossRefGoogle Scholar
  34. 34.
    Soleimannejad J, Aghabozorg H, Sheshmani S (2010) Acta Cryst E 66:m411CrossRefGoogle Scholar
  35. 35.
    Aghabozorg H, Nemati A, Derikvand Z, Ghadermazi M (2007) Acta Cryst E 63:m2921CrossRefGoogle Scholar
  36. 36.
    Aghabozorg H, Ghadermazi M, Zabihi F, Nakhjavan B, Soleimannejad J, Sadr-khanlou E, Moghimi A (2008) J Chem Crystallogr 38:645CrossRefGoogle Scholar
  37. 37.
    Aghabozorg H, Roshan L, Firoozi N, Bagheri S, Ghorbani Z, Kalami S, Mirzaei M, Shokrollahi A, Ghaedi M, Aghaei R, Ghadermazi M (2010) Struct Chem 21:701CrossRefGoogle Scholar
  38. 38.
    Yeşilel OZ, Mutlu A, Büyükgüngör O (2009) Polyhedron 28:437CrossRefGoogle Scholar
  39. 39.
    Li XH, Shi Q, Hu ML, Xiao HP (2004) Inorg Chem Commun 7:912CrossRefGoogle Scholar
  40. 40.
    Mao L, Rettig SJ, Thompson RC, Trotter J, Xia S (1996) Can J Chem 74:433CrossRefGoogle Scholar
  41. 41.
    Wang FQ, Zheng XJ, Sun YX (2009) Bull Korean Chem Soc 30:264CrossRefGoogle Scholar
  42. 42.
    Yin H, Liu SX (2007) Polyhedron 26:3103CrossRefGoogle Scholar
  43. 43.
    Bruker, APEX II software package, v. 1.27 (2005) Bruker molecular analysis research tool. Bruker AXS, Madison, WIGoogle Scholar
  44. 44.
    Stoe & Cie (2005) X-AREA. Stoe & Cie, DarmstadtGoogle Scholar
  45. 45.
    Sheldrick GM (2008) Acta Cryst A 64:112CrossRefGoogle Scholar
  46. 46.
    Sheldrick GM, SADABS, v. 2.03 (2003) Bruker/Siemens area detector absorption correction program. Bruker AXS, MadisonGoogle Scholar
  47. 47.
    Bruker, SAINT, v. 6.2 (2001) Data reduction and correction program. Bruker AXS, MadisonGoogle Scholar
  48. 48.
    Sheldrick GM, SHELXTL, v. 6.12 (2001) Structure determination software suite. Bruker AXS, MadisonGoogle Scholar
  49. 49.
    Aghabozorg H, Eshtiagh-Hosseini H, Salimi AR, Mirzaei M (2010) J Iran Chem Soc 72:89Google Scholar
  50. 50.
    Aghabozorg H, Sadr-Khanlou E, Shokrollahi A, Ghaedi M, Shamsipur M (2009) J Iran Chem Soc 6:55Google Scholar
  51. 51.
    Aghabozorg H, Ramezanipour F, Soleimannejad J, Sharif MA, Shokrollahi A, Shamsipur M, Moghimi A, Attar Gharamaleki J, Lippolis V, Blake AJ (2008) Polish J Chem 82:487Google Scholar
  52. 52.
    Aghajani Z, Aghabozorg H, Sadr-Khanlou E, Shokrollahi A, Derki S, Shamsipur M (2009) J Iran Chem Soc 6:373Google Scholar
  53. 53.
    Aghabozorg H, Manteghi F, Ghadermazi M, Mirzaei M, Salimi AR, Shokrollahi A, Derki S, Eshtiagh-Hosseini H (2009) J Mol Struct 919:381CrossRefGoogle Scholar
  54. 54.
    Mirzaei M, Eshtiagh-Hosseini H, Lippolis V, Aghabozorg H, Kordestani D, Shokrollahi A, Aghaei R, Blake AJ (2011) Inorg Chim Acta 370:141CrossRefGoogle Scholar
  55. 55.
    Eshtiagh-Hosseini H, Aghabozorg H, Mirzaei M, Beyramabadi SA, Eshghi H, Morsali A, Shokrollahi A, Aghaei R (2011) Spectrochim Acta 78A:1392Google Scholar
  56. 56.
    Martell AE, Motekaitis RJ (1992) Determination and use of stability constants, 2nd edn. VCH, New YorkGoogle Scholar
  57. 57.
    Joshaghani M, Sotodehnejad M (2003) Iran J Chem Chem Eng 22:17Google Scholar
  58. 58.
    Angyl SJ, Angyal CL (1952) J Chem Soc 1461Google Scholar
  59. 59.
    Wenkin M, Devillers M, Tinant B, Declercq JP (1997) Inorg Chim Acta 258:113CrossRefGoogle Scholar
  60. 60.
    English JB, Martell AE, Motekaitis RJ, Murase I (1997) Inorg Chim Acta 258:183CrossRefGoogle Scholar
  61. 61.
    Becke AD (1993) J Chem Phys 98:5648CrossRefGoogle Scholar
  62. 62.
    Frisch MJ et al (1998) Gaussian 98, revision A7. Gaussian, Inc., Pittsburgh, PAGoogle Scholar
  63. 63.
    Hay PJ, Wadt WR (1985) J Chem Phys 82:299CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2011

Authors and Affiliations

  • M. Mirzaei
    • 1
  • H. Eshtiagh-Hosseini
    • 1
  • N. Alfi
    • 1
  • H. Aghabozorg
    • 2
  • J. Attar Gharamaleki
    • 2
  • S. A. Beyramabadi
    • 3
  • H. R. Khavasi
    • 4
  • A. R. Salimi
    • 1
  • A. Shokrollahi
    • 5
  • R. Aghaei
    • 5
  • E. Karami
    • 5
  1. 1.Department of ChemistryFerdowsi University of MashhadMashhadIran
  2. 2.Faculty of ChemistryTarbiat Moallem UniversityTehranIran
  3. 3.Department of Chemistry, Faculty of ScienceIslamic Azad UniversityMashhadIran
  4. 4.Departement of ChemistryShahid Beheshti UniversityTehranIran
  5. 5.Department of ChemistryYasouj UniversityYasoujIran

Personalised recommendations