Skip to main content
SpringerLink
Log in

Synthesis, spectroscopy and cyclic voltammetry of new iron(III) complexes with 5-methyl-3-formyl pyrazole 3-hexamethyleneiminyl thiosemicarbazone (HMPz3Hex): X-ray crystallographic identification of [Fe(MPz3Hex)2]ClO4 · 2H2O with an indication for unusual rotation about the azomethine double bond on complexation with iron(III)

  • Published:
Transition Metal Chemistry Aims and scope Submit manuscript

Abstract

New iron(III) complexes of 5-methyl-3-formylpyrazole 3-hexamethyleneiminylthiosemicarbazone (HMPz3Hex), [Fe(MPz3Hex)2]X · nH2O (where X = Cl, NO3or ClO4 and n = 1–2) have been synthesized and physico-chemically characterized by magnetic data (polycrystalline state), electronic, i.r. and e.p.r. spectral studies. The reported complexes are all cationic electrolytes (1:1) containing two moles of monodeprotonated title ligand and an anionic counterpart. I.r. spectra (4000–200 cm−1) indicate coordination to the central iron(III) ion via the pyrazolyl (tertiary) ring nitrogen, azomethine nitrogen and thiolato sulphur atoms of the primary ligand molecule. E.p.r. data (r.t. and l.n.t.) show the presence of a low-spin iron(III) cation with d 2 xz d 2 xz d 1 xz configuration. Cyclic voltammograms of iron(III) complexes indicate a reversible Fe+3/Fe+2 couple. X-ray data of [Fe(MPz3Hex)2]ClO4 · 2H2O (P1, triclinic) authenticate a FeN4S2 distorted octahedral coordination with the two azomethine nitrogens trans to each other; the pyrazolyl nitrogens and thiolato sulphurs are in cis-positions, indicating an unusual rotation about the azomethine (C=N) double bond of the free HMPz3Hex during complexation with iron(III).

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.

Institutional subscriptions

Similar content being viewed by others

References

  1. DL. Klayman JF. Bartosevich TS. Griffin C.J. Mason JP. Scovill (1979) J. Med. Chem. 22 855

    Google Scholar 

  2. DX. West S.B. Padhye PB. Sonawane (1991) Struct. and Bonding. 76 1

    Google Scholar 

  3. A.E. Liberta DX. West (1992) Biometals. 5 121

    Google Scholar 

  4. FA. French SuffixJr. EJ. Blanz J.R. Do Amaral DA. French (1970) J. Med. Chem. 13 1117

    Google Scholar 

  5. R. Raina TS. Srivastava (1982) Inorg. Chim. Acta. 67 83

    Google Scholar 

  6. R. Raina TS. Srivastava (1983) Ind. J. Chem. 22 701

    Google Scholar 

  7. H. Beraldo L. Tosi (1983) Inorg. Chim. Acta. 75 249

    Google Scholar 

  8. P. Bera N. Saha S. Kumar D. Banerjee R. Bhattacharya (1999) Transition Met. Chem. 24 425

    Google Scholar 

  9. NC. Saha A. Saha RJ. Butcher S. Chaudhuri N. Saha (2002) Inorg. Chim. Acta. 339C 348

    Google Scholar 

  10. NC. Saha RJ. Butcher S. Chaudhuri N. Saha (2003) Polyhedron. 22 375

    Google Scholar 

  11. DK. Sau RJ. Butcher S. Chaudhuri N. Saha (2004) Polyhedron. 23 5

    Google Scholar 

  12. A. Mitra T. Banerjee P. Roychowdhury S. Chaudhuri P. Bera N. Saha (1997) Polyhedron. 16 3735

    Google Scholar 

  13. Bera P., Butcher R.J., Saha N. (1998). Chem. Lett. 559.

  14. NC. Saha A. Seal R.J. Butcher N. Saha (2001) J. Indian Chem. Soc. 78 601

    Google Scholar 

  15. P. Bera RJ. Butcher S. Chaudhuri N. Saha (2002) Polyhedron. 21 1

    Google Scholar 

  16. NC. Saha RJ. Butcher S. Chaudhuri N. Saha (2002) Polyhedron. 21 779

    Google Scholar 

  17. DK. Sau N. Saha R.J. Butcher S. Chaudhuri (2003) Transition Met. Chem. 28 229

    Google Scholar 

  18. DK. Sau RJ. Butcher S. Chaudhuri N. Saha (2003) Mol. Cell. Biochem. 253 21

    Google Scholar 

  19. DK. Sau N. Saha R.J. Butcher S. Chaudhuri (2004) Transition Met. Chem. 29 75

    Google Scholar 

  20. N. Saha N. Mukherjee (1984) Polyhedron. 3 1135

    Google Scholar 

  21. Sheldrick GM., SHELXS 97, Program for the Automatic Solution of Crystal Structures, Universität Göttingen, Göttingen, Germany, 1997; Sheldrick GM., SHELXL 97, Program for The Refinement of Crystal Structure, Universität Göttingen, Göttingen, Germany, 1997.

  22. D.T. Cromer JT. Weber (1994) International Tables for X-ray Crystallography The Keynoch Press Birmingham, England

    Google Scholar 

  23. J.A. Ibers WC. Hamilton (1964) Acta. Crystallogr. 17 781

    Google Scholar 

  24. LJ. Farrugia (1997) J. Appl. Crystallogr. 30 565

    Google Scholar 

  25. WJ. Geary (1971) Coord. Chem.Rev. 7 81

    Google Scholar 

  26. R.C. Agarwal TR. Rao (1978) J. Inorg. Nucl. Chem. 40 1177

    Google Scholar 

  27. JR. Ferraro (1969) Appl. Spectrosc. 23 60

    Google Scholar 

  28. AH. Ewald RL. Martin E. Sinn AH. White (1969) Inorg. Chim. Acta. 8 1837

    Google Scholar 

  29. FA. Cotton (1972) Coord. Chem. Rev. 8 185

    Google Scholar 

  30. R. Raina TS. Srivastava (1984) Inorg. Chim. Acta. 91 137

    Google Scholar 

  31. DX. West PM. Ahweiler G. Ertem JP. Scovill DL. Klaymann J.L. Flippen- Andeson R. Gilardi C. George LK. Pannell (1985) Transition Met. Chem. 10 264

    Google Scholar 

  32. BS. Garg M.RP. Kurup S.K. Jain YK. Bhoon (1988) Transition Met. Chem. 13 247

    Google Scholar 

  33. SK. Jain B.S. Garg YK. Bhoon (1986) Transition Met. Chem. 11 89

    Google Scholar 

  34. SK. Jain B.S. Garg YK. Bhoon (1986) Spectrochim. Acta. 42A 959

    Google Scholar 

  35. K. Nishida S. Oshio S. Kida (1977) Inorg. Chim. Acta. 23 59

    Google Scholar 

  36. O. Seidelmann L. Beyer (1998) Polyhedron. 17 1601

    Google Scholar 

  37. A.J. Bard LR. Faulkner (1980) Electrochemical Methods (Fundamentals and Applications) John Wiley & Sons Inc. USA 259

    Google Scholar 

  38. R. Nicholson I. Shain (1964) Analytical Chem. 36 706

    Google Scholar 

  39. K. Saraswati K. Yamuna P. Prameela (1998) J. Indian Chem. Soc. 75 130

    Google Scholar 

  40. Mandal PC., J. Electroanal. Chem., (2004) in press.

Download references

Author information

Author notes

  1. Dhiman Kumar Sau

    Present address: Baidyapota, D.C. Rakshit Road, P.O. Chandernagore Dist. Hoogly, Pin-712136, West Bengal, India

Authors and Affiliations

  1. Department of Chemistry, University of Calcutta, 92, A P C Road, Kolkata, 700 009, India

    Nityananda Saha & Dhiman Kumar Sau

  2. SAIF, Bose Institute, Kolkata, 700 009, India

    Siddhartha Chaudhuri

  3. Chemical Sciences Division, Saha Institute of Nuclear Physics, Kolkata, 700 064, India

    Parikshit Chandra Mandal

Authors
  1. Nityananda Saha
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dhiman Kumar Sau
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Siddhartha Chaudhuri
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Parikshit Chandra Mandal
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Nityananda Saha-Deceased.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Saha, N., Sau, D.K., Chaudhuri, S. et al. Synthesis, spectroscopy and cyclic voltammetry of new iron(III) complexes with 5-methyl-3-formyl pyrazole 3-hexamethyleneiminyl thiosemicarbazone (HMPz3Hex): X-ray crystallographic identification of [Fe(MPz3Hex)2]ClO4 · 2H2O with an indication for unusual rotation about the azomethine double bond on complexation with iron(III). Transition Met Chem 30, 532–540 (2005). https://doi.org/10.1007/s11243-005-1029-y

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11243-005-1029-y

Keywords

Search

Navigation