Skip to main content
SpringerLink
Log in

Synthesis, X-ray structure, and DFT modeling of a new polymeric zinc(II) complex of 2-mercaptonicotinic acid (MntH), {[Zn(Mnt–Mnt)(en)]·H2O}n

  • Original Paper
  • Published:
Monatshefte für Chemie - Chemical Monthly Aims and scope Submit manuscript

Abstract

Two zinc(II) complexes of 2-mercaptonicotinic acid (MntH), {[Zn(Mnt–Mnt)(en)]·H2O}n and [Zn(Mnt–Mnt)(H2O)], were prepared by the reaction of ZnCl2 and MntH in the presence of ethylenediamine (en). They were characterized by elemental analysis, and IR, 1H, 13C NMR and UV–Vis spectroscopic studies. In the presence of en, the sulfur atoms of the MntH ligands were connected and formed a disulfide linkage in the Mnt–Mnt dimer. The single crystal X-ray diffraction analysis of {[Zn(Mnt–Mnt)(en)]·H2O}n complex revealed the polymer structure organization. Each zinc atom is five coordinated in distorted trigonal bipyramidal polyhedron by three oxygen atoms of two bridging Mnt–Mnt ligands and two nitrogen atoms of an en molecule. The vibrational modes, which characterized the carboxylic oxygen coordination of the Mnt–Mnt ligand to Zn(II), were determined by periodic DFT/PAW/PW91 calculations. Molecular structure modeling, vibrational spectra calculations, and natural bond orbital analysis of the monomer and dimer ligands as well as of the Zn(II) complexes were performed at the DFT/TDDFT/mPW1PW91 level to explain the available IR, NMR and UV–Vis spectroscopic data and to confirm the ligand coordination to the metal ion. The formation of disulfide Mnt–Mnt ligand in [Zn(Mnt–Mnt)(H2O)] was confirmed by the absence of the absorption band at 377 nm in the UV–Vis spectrum. The molecular modeling fragment of [Zn(Mnt–MntH)2(H2O)] suggested that the most probable structure is that consisting of five coordinated Zn(II) with one aqueous oxygen and four carboxylic oxygens of two bidentate bound Mnt–Mnt ligands in a polymeric structure.

Graphical abstract

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Kaim W, Schwederski B (1994) Bioinorganic chemistry: inorganic elements in the chemistry of life, an introduction and guide. Wiley, New Jersey

    Google Scholar 

  2. Williams RJP (1987) Polyhedron 6:61

    Article  CAS  Google Scholar 

  3. Sousa SF, Lopes AB, Fernandes PA, Ramos MJ (2009) Dalton Trans 38:7946

    Article  Google Scholar 

  4. Maret W (2012) J Inorg Biochem 111:110

    Article  CAS  Google Scholar 

  5. Auld DS (2001) Biometals 14:271

    Article  CAS  Google Scholar 

  6. Alberts IL, Nadassy K, Wodak SJ (1998) Protein Sci 7:1700

    Article  CAS  Google Scholar 

  7. Lipscomb WN, Strater N (1996) Chem Rev 96:2375

    Article  CAS  Google Scholar 

  8. Strater N, Lipscomb WN, Klabunde T, Krebs B (1996) Angew Chem Int Ed 35:2024

    Article  Google Scholar 

  9. Koziol L, Valdez CA, Baker SE, Lau EY, Floyd WC, Wong SE, Satcher JH, Lightstone FC, Aines RD (2012) Inorg Chem 51:6803

    Article  CAS  Google Scholar 

  10. Ye BH, Li XY, Williams ID, Chen XM (2002) Inorg Chem 41:6426

    Article  CAS  Google Scholar 

  11. Strater N, Lipscomb WN (1995) Biochem 34:14792

    Article  CAS  Google Scholar 

  12. Kumar U, Singh M, Thirupathi N (2013) Polyhedron 55:233

    Article  CAS  Google Scholar 

  13. Vahrenkamp H (2007) Dalton Trans 42:4751

    Article  Google Scholar 

  14. Rardin RL, Tolman WB, Lippard SJ (1991) New J Chem 15:417

    CAS  Google Scholar 

  15. Chun H, Dybtsev DN, Kim H, Kim K (2005) Chem Eur J 11:3521

    Article  CAS  Google Scholar 

  16. Crees RS, Cole ML, Hanton LR, Sumby CJ (2010) Inorg Chem 49:1712

    Article  CAS  Google Scholar 

  17. Dutta B, Bag P, Florke U, Nag K (2005) Inorg Chem 44:147

    Article  CAS  Google Scholar 

  18. Sheng GH, Cheng XS, You ZL, Zhu HL (2014) Bull Chem Soc Ethiop 28:315

    Article  Google Scholar 

  19. Liu YL, Yue KF, Shan BH, Xu LL, Wang CJ, Wang YY (2012) Inorg Chem Commun 17:30

    Article  CAS  Google Scholar 

  20. Katsoulakou E, Dermitzaki D, Konidaris KF, Moushi EE, Raptopoulou CP, Psycharis V, Tasiopoulos AJ, Bekiari V, Manessi-Zoupa E, Perlepes SP, Stamatatos TC (2013) Polyhedron 52:467

    Article  CAS  Google Scholar 

  21. Di Marco VB, Tapparo A, Dolmella A, Bombi GG (2004) Inorg Chim Acta 357:135

    Article  Google Scholar 

  22. Goher MAS, Abu-Youssef MAM, Mautner FA (1996) Polyhedron 15:453

    Article  CAS  Google Scholar 

  23. Abu-Youssef MAM (2005) Polyhedron 24:1829

    Article  CAS  Google Scholar 

  24. Darawsheh M, Abu Ali H, Abuhijleh AL, Rappocciolo E, Akkawi M, Jaber S, Maloul S, Hussein Y (2014) Eur J Med Chem 82:152

    Article  CAS  Google Scholar 

  25. Abu Ali H, Darawsheh MD, Rappocciolo E (2013) Polyhedron 61:235

    Article  CAS  Google Scholar 

  26. Radovanovic L, Rogan J, Poleti D, Milutinovic M, Rodic MV (2016) Polyhedron 112:18

    Article  CAS  Google Scholar 

  27. Muhammad N, Ikram M, Wadood A, Rehman S, Shujah S, Erum, Ghufran M, Rahim S, Shah M, Schulzke C (2018) Spectrochim Acta A 190:368

    Article  CAS  Google Scholar 

  28. Akhtar M, Alotaibi MA, Alharthi AI, Zierkiewicz W, Tahir MN, Mazhar M, Isab AA, Monim-ul-Mehboob M, Ahmad S (2017) J Mol Struct 1128:455

    Article  CAS  Google Scholar 

  29. Alotaibi MA, Alharthi AI, Zierkiewicz W, Akhtar M, Tahir MN, Mazhar M, Isab AA, Ahmad S (2017) J Mol Struct 1133:271

    Article  CAS  Google Scholar 

  30. Malik MR, Vasylyeva V, Merz K, Metzler-Nolte N, Saleem M, Ali S, Isab AA, Munawar KS, Ahmad S (2011) Inorg Chim Acta 376:207

    Article  CAS  Google Scholar 

  31. Akhtar M, Tahir MN, Saleem M, Mazhar M, Rauf A, Isab AA, Ahmad S, Nadeem S (2015) Russ J Inorg Chem 60:1568

    Article  CAS  Google Scholar 

  32. Akhtar M, Alharthi AI, Alotaibi MA, Trendafilova N, Georgieva N, Tahir MN, Mazhar M, Isab AA, Hanif M, Ahmad S (2017) Polyhedron 122:105

    Article  CAS  Google Scholar 

  33. Ahmad T, Mahmood R, Georgieva I, Zahariev T, Tahir MN, Shaheen MA, Gilani MA, Ahmad S (2018) J Mol Struct 1153:179

    Article  CAS  Google Scholar 

  34. Ahmad S, Espinosa A, Ahmad T, Sohail M, Isab AA, Saleem M, Hameed A, Monim-ul-Mehboob M, de las Heras E (2015) Polyhedron 85:239

    Article  CAS  Google Scholar 

  35. Sheldrick GM (2008) Acta Cryst A 64:112

    Article  CAS  Google Scholar 

  36. Sheldrick GM (2015) Acta Cryst C 71:3

    Article  Google Scholar 

  37. Spek AL (2009) Acta Cryst D 65:148

    Article  CAS  Google Scholar 

  38. Kresse G, Hafner J (1993) Phys Rev B 47:558

    Article  CAS  Google Scholar 

  39. Kresse G, Hafner J (1994) Phys Rev B 49:14251

    Article  CAS  Google Scholar 

  40. Kresse G, Furthmuller J (1996) Phys Rev B 54:11169

    Article  CAS  Google Scholar 

  41. Blochl PE (1994) Phys Rev B 50:17953

    Article  CAS  Google Scholar 

  42. Kresse G, Joubert D (1999) Phys Rev B 59:1758

    Article  CAS  Google Scholar 

  43. Baroni S, de Gironcoli S, Dal Corso A, Giannozzi P (2001) Rev Mod Phys 73:515

    Article  CAS  Google Scholar 

  44. Wu X, Vanderbilt D, Hamann DR (2005) Phys Rev B 72:035105

    Article  Google Scholar 

  45. Gajdos M, Hummer K, Kresse G, Furthmuller J, Bechstedt F (2006) Phys Rev B 73:045112

    Article  Google Scholar 

  46. Karhanek D, Bucko T, Hafner J (2010) J Phys: Condens Matter 22:265006

    Google Scholar 

  47. Zachariadis PC, Hadjikakou SK, Hadjiliadis N, Michaelides A, Skoulika S, Ming Y, Yu XL (2003) Inorg Chim Acta 343:361

    Article  CAS  Google Scholar 

  48. Adamo C, Barone V (1998) J Chem Phys 108:664

    Article  CAS  Google Scholar 

  49. Barone V, Cossi M (1998) J Phys Chem A 102:1995

    Article  CAS  Google Scholar 

  50. Cossi M, Rega N, Scalmani G, Barone V (2003) J Comput Chem 24:669

    Article  CAS  Google Scholar 

  51. Weinhold F, Carpenter JE (1988) J Mol Struct THEOCHEM 42:189

    Article  CAS  Google Scholar 

  52. 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 D.01. Gaussian, Inc., Wallingford

    Google Scholar 

  53. Andrienko GA, Chemcraft program - graphical software for visualization of quantum chemistry computations, Version 1.8 (build 536b, 01/05/2018); https://www.chemcraftprog.com

Download references

Acknowledgements

The DFT calculations were performed on the MADARA computer cluster of the Bulgarian Academy of Sciences, supported by Grant RNF01/0110 from the National Science Fund (NSFB). I.G., N.T., and T. Z. thank the National Science Fund of the Bulgarian Ministry of Education and Science for the financial support under Grant no, DH09/9.

Author information

Authors and Affiliations

  1. Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan

    Muhammad Akhtar

  2. Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 11 Acad. G. Bonchev Str., 1113, Sofia, Bulgaria

    Ivelina Georgieva, Tsvetan Zahariev & Natasha Trendafilova

  3. Department of Chemistry, University of Engineering and Technology, Lahore, 54890, Pakistan

    Tayyaba Ahmad & Aqeela Noor

  4. Department of Physics, University of Sargodha, Sargodha, Pakistan

    Muhammad Nawaz Tahir

  5. Department of Environmental Sciences, Faculty of Science, Fatima Jinnah Women University, Rawalpindi, Pakistan

    Muhammad Mazhar

  6. Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran, 31261, Saudi Arabia

    Anvarhusein A. Isab

  7. Department of Chemistry, College of Sciences and Humanities, Prince Sattam Bin Abdulaziz University, Al-Kharj, 11942, Saudi Arabia

    Saeed Ahmad

Authors
  1. Muhammad Akhtar
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ivelina Georgieva
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Tsvetan Zahariev
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Natasha Trendafilova
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Tayyaba Ahmad
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Aqeela Noor
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Muhammad Nawaz Tahir
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Muhammad Mazhar
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Anvarhusein A. Isab
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Saeed Ahmad
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Ivelina Georgieva or Saeed Ahmad.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 3642 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Akhtar, M., Georgieva, I., Zahariev, T. et al. Synthesis, X-ray structure, and DFT modeling of a new polymeric zinc(II) complex of 2-mercaptonicotinic acid (MntH), {[Zn(Mnt–Mnt)(en)]·H2O}n. Monatsh Chem 150, 219–231 (2019). https://doi.org/10.1007/s00706-018-2330-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00706-018-2330-8

Keywords

Search

Navigation