Chemical Papers

, Volume 72, Issue 4, pp 903–919 | Cite as

Synthesis, spectroscopic characterization, X-ray structure, DFT calculations, and antimicrobial studies of diorganotin (IV) complexes of monotopic oxygen nitrogen donor Schiff base

  • Shaukat Shujah
  • Saqib Ali
  • Nasir Khalid
  • Mohammad Jane Alam
  • Shabbir Ahmad
  • Auke Meetsma
Original Paper


Seven new diorganotin(IV) complexes, [Me2SnL] (1), [Et2SnL] (2), [(n-Bu2SnL] (3), [Ph2SnL] (4), [(n-Oct2SnL] (5), [tert-Bu2SnL] (6), and [n-BuClSnL] (7) have been synthesized from the reaction of N′-(2-hydroybenzylidene)-4-tert-butylbenzohydrazide (H2L) with the corresponding diorganotin(IV) dichloride/oxide or organotin(IV) chloride dihydroxide. The synthesized compounds were structurally characterized by FT-IR, multinuclear NMR (1H and 13C) spectroscopies, elemental analysis, mass spectrometry, DFT/(B3LYP) calculations, and, for ligand single crystal, X-ray diffraction analysis. Spectroscopic evidence affirms coordination of ligand to the dialkyltin(IV) moieties through oxygen nitrogen donor sites in iminol form. The 1 J(119Sn, 13C) coupling constants, 584-655 Hz and 2 J(119Sn-1H) coupling constant, 79 Hz for complex (1), suggest pentacoordination around Sn atom in solution. Single-crystal X-ray structure of ligand show its existence in amido form. Supramolecular architecture mediated by N(2)-H···O(2) and C-H…π interactions is formed in solid state. The DFT calculations have been performed to obtain various structure-based molecular properties as well as to support experimental results. The synthesized compounds were screened in vitro against various human pathogenic microbial strains. Escherichia coli and Staphylococcus aureus were most visibly inhibited by complexes (4) and (7). Highest antifungal activity was shown by compound (6) against Fusarium solani. Compound (3) displayed highest cytotoxicity among synthesized compounds with LD50 0.44μg/mL.

Graphical Abstract


Diorganotin(IV) complexes DFT calculations Antibacterial activity Antifungal Activity Cytotoxicity 



The authors are thankful to Higher Education Commission of Pakistan for the financial support.

Supplementary material

11696_2017_333_MOESM1_ESM.docx (7.5 mb)
Supplementary material: CCDC reference number 993525 contains the supplementary crystallographic data for N′-(2-hydroxybenzylidene)-4-tert-butylbenzohydrazide (H2L). These data can be obtained free of charge from The Cambridge Crystallographic Data Center via Electronic Supplementary Material associated with this article can be found in the online version of this paper (DOI: xxxxxxxxxx) (DOCX 7686 kb)


  1. Anwer J, Ali S, Shahzadi S, Shahid M, Sharma SK, Qanungo K (2013) Synthesis, characterization, semi-empirical study and biological activities of homobimetallic complexes of tranexamic acid with organotin(IV). J Coord Chem 66:1142–1152. CrossRefGoogle Scholar
  2. Armarego WL, Chai CLL (2013) Purification of laboratory chemicals. Butterworth-Heinemann, USAGoogle Scholar
  3. Atta-ur-Rahman CM, Thomsen WJ (2001) Bioassay techniques for drug development. Harwood Academic Publishers, The NetherlandsCrossRefGoogle Scholar
  4. Ayers PW, Anderson JS, Bartolotti LJ (2005) Perturbative perspectives on the chemical reaction prediction problem. Int J Quantum Chem 101:520–534. CrossRefGoogle Scholar
  5. Ayoko GA, Bonire JJ, Abdulkadir SS, Olurinola PF, Ehinmidu JO, Kokot S, Yiasel S (2003) A multicriteria ranking of organotin(IV) compounds with fungicidal properties. Appl Organomet Chem 17:749–758. CrossRefGoogle Scholar
  6. Becke AD (1988) Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A 38:3098. CrossRefGoogle Scholar
  7. Beurskens P, Beurskens G, De Gelder R, Garcia-Granda S, Gould R, Israel R, Smits J (1999) The DIRDIF-99 program system. Crystallography Laboratory, University of Nijmegen, NijmegenGoogle Scholar
  8. Borba A, Albrecht M, Gómez-Zavaglia A, Suhm MA, Fausto R (2010) Low temperature infrared spectroscopy study of pyrazinamide: from the isolated monomer to the stable low temperature crystalline phase. J Phys Chem A 114:151–161. CrossRefGoogle Scholar
  9. Bruker S (2006) SAINTPLUS and XPREP. Area Detector Control and Integration Software. Smart Apex Software Reference Manuals. Bruker Analytical X-ray Instruments Inc, MadisonGoogle Scholar
  10. Chaudhary P, Swami M, Sharma D, Singh R (2009) Ecofriendly synthesis, antimicrobial and antispermatogenic activity of triorganotin (IV) complexes with 4′-nitrobenzanilide semicarbazone and 4′-nitrobezanilide thiosemicarbazone. Appl Organomet Chem 23:140–149. CrossRefGoogle Scholar
  11. Chermette H (1999) Chemical reactivity indexes in density functional theory. J Comput Chem 20:129–154.<129:AID-JCC13>3.0.CO;2-A CrossRefGoogle Scholar
  12. Dennington R, Keith T, Millam JG (2009) GaussView, Ver. 5.0.9 Semichem Inc, Shawnee Mission KS USAGoogle Scholar
  13. Fani S, Kamalidehghan B, Lo KM, Hashim NM, Chow KM, Ahmadipour F (2015) Synthesis, structural characterization, and anticancer activity of a monobenzyltin compound against MCF-7 breast cancer cells. Drug Des Devel Ther 9:6191–6201. CrossRefGoogle Scholar
  14. Finney D (1971) Probit analysis, 3rd edn. Cambridge University Press, LondonGoogle Scholar
  15. Frisch M et al. (2009) Gaussian 09, revision D. 01. Gaussian, Inc., Wallingford CTGoogle Scholar
  16. Fukushima K, Dubey SK, Suzuki S (2012) YgiW homologous gene from Pseudomonas aeruginosa 25 W is responsible for tributyltin resistance. J Gen Appl Microbiol 58:283–289. CrossRefGoogle Scholar
  17. Geerlings P, De Proft F (2008) Conceptual DFT: the chemical relevance of higher response functions. PCCP 10:3028–3042. CrossRefGoogle Scholar
  18. Geerlings P, De Proft F, Langenaeker W (2003) Conceptual density functional theory. Chem Rev 103:1793–1874. CrossRefGoogle Scholar
  19. Gholivand K, EbrahimiValmoozi AA, Gholami A, Dusek M, Eigner V, Abolghasemi S (2016) Synthesis, characterization, crystal structures, QSAR study and antibacterial activities of organotin bisphosphoramidates. J Organomet Chem 806:33–44. CrossRefGoogle Scholar
  20. Girasolo MA, Attanzio A, Sabatino P, Tesoriere L, Rubino S, Stocco G (2014) Organotin(IV) derivatives with 5,7-disubstituted-1,2,4-triazolo[1,5-a]pyrimidine and their cytotoxic activities: the importance of being conformers. Inorg Chim Acta 423(Part B):168–176. CrossRefGoogle Scholar
  21. Holeček J, Lyčka A (1986) Dependence of| 1J (119Sn13C)| on the C- Sn- C angle in n-butyltin (IV) compounds. Inorg Chim Acta 118:L15–L16CrossRefGoogle Scholar
  22. Hong M, Yin H-D, Cui J-C (2011) Weakly-bridged dimeric diorganotin (IV) compounds derived from pyruvic acid hydrazone Schiff base ligands: synthesis, characterization and crystal structures. Solid State Sci 13:501–507. CrossRefGoogle Scholar
  23. Kohn W, Becke AD, Parr RG (1996) Density functional theory of electronic structure. J Phys Chem 100:12974–12980. CrossRefGoogle Scholar
  24. Kovala-Demertzi D, Dokorou V, Primikiri A, Vargas R, Silvestru C, Russo U, Demertzis MA (2009) Organotin meclofenamic complexes: synthesis, crystal structures and antiproliferative activity of the first complexes of meclofenamic acid—Novel anti-tuberculosis agents. J Inorg Biochem 103:738–744. CrossRefGoogle Scholar
  25. Lee C, Yang W, Parr R (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B: Condens Matter 37(2):785–789CrossRefGoogle Scholar
  26. Lockhart TP, Manders WF (1986) Structure determination by NMR spectroscopy. Dependence of| 2J (119Sn, 1H)| on the Me-Sn-Me angle in methyltin(IV) compounds. Inorg Chem 25:892–895. CrossRefGoogle Scholar
  27. Meetsma A (2001) PLUTO. Molecular graphics program. University of Groningen, The NetherlandsGoogle Scholar
  28. Muhammad N, Zia-Ur-Rehman Shujah S, Shah A, Ali S, Meetsma A, Hussain Z (2012) Syntheses, structural characteristics, and antimicrobial activities of new organotin (IV) 3-(4-bromophenyl)-2-ethylacrylates. J Coord Chem 65:3766–3775. CrossRefGoogle Scholar
  29. Parr R, Yang W (1989) Density functional theory of atoms and molecules. Oxford Univ Press, New YorkGoogle Scholar
  30. Parr RG, Yang W (1995) Density-functional theory of the electronic structure of molecules. Annu Rev Phys Chem 46:701–728. CrossRefGoogle Scholar
  31. Pettinari C, Marchetti F, Pettinari R, Martini D, Drozdov A, Troyanov S (2001) Synthesis and characterisation of tin (IV) and organotin (IV) derivatives 2-{[(2-hydroxyphenyl) imino] methyl} phenol. Inorg Chim Acta 325:103–114. CrossRefGoogle Scholar
  32. Rehman W, Baloch MK, Badshah A (2008) Synthesis, spectral characterization and bio-analysis of some organotin (IV) complexes. Eur J Med Chem 43:2380–2385. CrossRefGoogle Scholar
  33. Roy M, Roy S, Singh KS, Kalita J, Singh SS (2016) Synthesis, characterisation and anti-diabetic activities of triorganotin (IV) azo-carboxylates derived from amino benzoic acids and resorcinol: crystal structure and topological study of a 48 membered macrocyclic-tetrameric trimethyltin(IV) complex. Inorg Chim Acta 439:164–172. CrossRefGoogle Scholar
  34. Sharma S, Meena R, Singh RV, Fahmi N (2016) Synthesis, characterization, antimicrobial, and DNA cleavage evaluation of some organotin(IV) complexes derived from ligands containing the 1H-indole-2,3-dione moiety. Main Group Met Chem 39:31–40. CrossRefGoogle Scholar
  35. Sheldrick G (1997) SHELX-97: Programs for crystal structure analysis Göttingen, GermanyGoogle Scholar
  36. Shpakovsky D et al (2014) Synthesis, antiradical activity and in vitro cytotoxicity of novel organotin complexes based on 2, 6-di-tert-butyl-4-mercaptophenol. Dalton Trans 43:6880–6890. CrossRefGoogle Scholar
  37. Shujah S, Muhammad N, Ali S, Khalid N, Tahir MN (2011) New dimeric and supramolecular organotin (IV) complexes with a tridentate schiff base as potential biocidal agents. J Organomet Chem 696:2772–2781. CrossRefGoogle Scholar
  38. Shujah S, Muhammad N, Shah A, Ali S, Khalid N, Meetsma A (2013) Bioactive hepta-and penta-coordinated supramolecular diorganotin (IV) Schiff bases. J Organomet Chem 741:59–66. CrossRefGoogle Scholar
  39. Sirajuddin M, Ali S, McKee V, Zaib S, Iqbal J (2014) Organotin(iv) carboxylate derivatives as a new addition to anticancer and antileishmanial agents: design, physicochemical characterization and interaction with Salmon sperm DNA. RSC Adv 4:57505–57521. CrossRefGoogle Scholar
  40. Spek A (1998) PLATON. Program for the Automated Analysis of Molecular GeometryGoogle Scholar
  41. Tariq M, Ali S, Muhammad N, Shah NA, Sirajuddin M, Tahir MN, Khalid N, Khan MR (2014) Biological screening, DNA interaction studies, and catalytic activity of organotin (IV) 2-(4-ethylbenzylidene) butanoic acid derivatives: synthesis, spectroscopic characterization, and X-ray structure. J Coord Chem 67:323–340. CrossRefGoogle Scholar
  42. Zhang Y-Y, Zhang R-F, Zhang S-L, Cheng S, Li Q-L, Ma C-L (2016) Syntheses, structures and anti-tumor activity of four new organotin(iv) carboxylates based on 2-thienylselenoacetic acid. Dalton Trans 45:8412–8421. CrossRefGoogle Scholar
  43. Zia ur R, Muhammad N, Shuja S, Ali S, Butler IS, Meetsma A, Khan M (2009) New dimeric, trimeric and supramolecular organotin(IV) dithiocarboxylates: synthesis, structural characterization and biocidal activities. Polyhedron 28:3439–3448. CrossRefGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2017

Authors and Affiliations

  1. 1.Department of ChemistryKohat University of Science and TechnologyKohatPakistan
  2. 2.Department of ChemistryQuaid-i-Azam UniversityIslamabadPakistan
  3. 3.Chemistry DivisionPakistan Institute of Nuclear Science and TechnologyIslamabadPakistan
  4. 4.Department of PhysicsAligarh Muslim UniversityAligarhIndia
  5. 5.Chemical Physics, Crystal Structure Center, Zernike Institute for Advanced MaterialsUniversity of GroningenGroningenThe Netherlands

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