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cis–trans Isomerism at Square-Planar MN2S2 Centers (M = Pd, Pt): Crystal Structures of N-Phenyl-N-(2-thiazoyl)thiourea Complexes trans-Pd(S2N3C10H8)2 and cis-Pt(S2N3C10H8)2 and Density Functional Calculations

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Abstract

Simple palladium(II) and platinum(II) complexes, ML2 (1–2), of N-phenyl-(2-thiazoyl)thiourea have been prepared and fully characterized. The structure of Pd(S2N3C10H8)2 (1) is monoclinic P21 /c, a = 12.510(2), b = 5.6963(6), c = 15.322(2) Å, b = 90.07(2)o and Pt(S2N3C10H8)2 (2) is orthorhombic P2 1 2 1 2 1 , a = 7.3021(5), b = 11.8025(9), c = 25.628(2) Å. In both complexes the ligands bind in a chelate fashion through the nitrogen atom of the thiazole ring and the sulfur atom of the thiourea to give six-membered chelate rings. In 1 the metal ion sits on an inversion center and the two ligands adopt a relative trans-disposition of like atoms, while in 2 all atoms are unique and the ligands are in a relative cis-disposition. DFT calculations on the cis and trans isomers based on 1 and 2 reveal that each pair of isomers is isoenergetic in the gas phase.

Graphical Abstract

Simple palladium(II) and platinum(II) complexes, M(S2N3C10H8)2, of N-Phenyl-(2-thiazoyl)thiourea have been prepared and fully characterized. In both complexes the ligands bind in a chelate fashion through the nitrogen atom of the thiazole ring and the sulfur atom of the thiourea to give six-membered chelate rings. In the palladium complex the metal ion sits on an inversion center and the two ligands adopt a relative trans-disposition of like atoms, while for platinum all atoms are unique and the ligands are in a relative cis-disposition. DFT calculations on the cis and trans isomers based on 1 and 2 reveal that each pair of isomers is isoenergetic in the gas phase.

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References

  1. Jadot J, Casimir J, Warin R (1969) Bull Soc Chim Belg 78:299

    Article  CAS  Google Scholar 

  2. Yamasa Y, Seki N, Kitahari T, Takahashi M, Matsui M (1970) Agri Biol Chem Jpn 35:780

    Google Scholar 

  3. Vitzhum OG, Werkhoff PJ (1974) Food Sci 39:1210

    Article  Google Scholar 

  4. Walradt JP, Pittet AO, Kinlin TE, Muralidhara R, Sanderson A (1971) J Agri Food Chem 19:972

    Article  CAS  Google Scholar 

  5. Krist HA, Szymanski EF, Dorman DE, Occolowitz JC, Jones ND, Jones MO, Chanery MO, Hamil RL, Hochn MM (1975) J Antibiot 28:286

    Article  Google Scholar 

  6. Brookes P, Fuller AT, Walker J (1957) J Chem Soc 689

  7. Goodin S, Kane MP, Rubin EH (2004) J Clin Oncol 22:2015

    Article  CAS  Google Scholar 

  8. Boulikas T, Vougiouka M (2003) Oncol Rep 10:1663

    CAS  Google Scholar 

  9. Go RS, Adjei AA (1999) Am Soc Clin Oncology 17:411

    Google Scholar 

  10. Raymond E, Chaney SG, Taamma A, Cvitkovic E (1998) Annals Oncology 9:1053

    Article  CAS  Google Scholar 

  11. Abu-Surah AS, Al-Sa’doni HH, Abdalla MY (2008) Cancer Therapy 6:1

    Google Scholar 

  12. Puthraya KH, Srivastava TS, Amonkar AJ, Adwankar MK, Chitnis MP (1986) J Inorg Biochem 26:45

    Article  CAS  Google Scholar 

  13. Mital R, Srivastava TS, Parekh HK, Chitnis MP (1991) J Inorg Biochem 41:93

    Article  CAS  Google Scholar 

  14. Jin VX, Ranford JD (2000) Inorg Chim Acta 304:38

    Article  CAS  Google Scholar 

  15. El-Sherif AA (2011) J Coord Chem 64:2035

    Article  CAS  Google Scholar 

  16. Ulukaya E, Ari F, Dimas K, Ikitimur EI, Guney E, Yilmaz VT (2011) Eur J Med Chem 46:4957

    Article  CAS  Google Scholar 

  17. Das M, Livingstone SE (1978) Br J Cancer 37:466

    Article  CAS  Google Scholar 

  18. Al-Jibori SA, Al-Saraj EGH, Hollingsworth N, Hogarth G (2012) Polyhedron 44:210

    Article  CAS  Google Scholar 

  19. Al-Jibori SA, Khaleel TF, Ahmed SAO, Al-Hayaly LJ, Merzweiler K, Wagner C, Hogarth G (2012) Polyhedron 41:20

    Article  CAS  Google Scholar 

  20. Al-Jibori SA, Al-Jibori MHS, Hogarth G (2013) Inorg Chim Acta 398:117

    Article  CAS  Google Scholar 

  21. Al-Jibori SA, Al-Nassiry AIA, Hogarth G, Salassa L (2013) Inorg Chim Acta 398:46

    Article  CAS  Google Scholar 

  22. Shoukry MM, Aziz K, Shoukry EM, Hamdallah S (1989) Transition Met Chem 14:115

    Article  CAS  Google Scholar 

  23. Singhal S, Chandak P, Mathur SP (1997) J Ind Chem Soc 74:695

    CAS  Google Scholar 

  24. Chandak P, Singhal S, Mathur SP (1997) Ind J Chem Sect A 36:453

    Google Scholar 

  25. Saleh MS, Khafagy ZA (1997) Afinidad 54:147

    CAS  Google Scholar 

  26. El-Gyar SA, Salman MH, Khafag ZA (1993) Bull Fac Sci Assiut Univ B 22:17

    CAS  Google Scholar 

  27. Madhok KL, Gupta C (1990) Polyhedron 9:2449

    Article  CAS  Google Scholar 

  28. IPDS-Software Package, Stoe and Cie, 1999

  29. Sheldrick GM (1997) SHELXS-97, Program for crystal structure, Göttingen

  30. Sheldrick GM (1997) SHELXS-97, Program for Refinement of Crystal Structures, Göttingen

  31. M J Frisch et al. (2009) Gaussian 09, Revision A.02, Gaussian, Inc. Wallingford CT

  32. Becke AD (1993) J Chem Phys 98:5648

    Article  CAS  Google Scholar 

  33. Lee C, Yang W, Parr RG (1988) Phys Rev B37:785

    Google Scholar 

  34. Reed AE, Curtiss LA, Weinhold F (1988) Chem Rev 88:899

    Article  CAS  Google Scholar 

  35. Wilberg KB (1968) Tetrahedron 24:1083

    Article  Google Scholar 

  36. Hall MB, Fenske RF (1972) Inorg Chem 11:768

    Article  CAS  Google Scholar 

  37. Manson J, Webster CE, Hall MB (2006) Texas A&M University, College Station, TX, http://www.chem.tamu.edu/jimp2/index.html

  38. Chatt J, Wilkins RG (1952) J Chem Soc 273:Ibid 4300

    Google Scholar 

  39. Anderson GK, Cross RJ (1980) Chem Soc Rev 9:185

    Article  CAS  Google Scholar 

  40. Harvey JN, Heslop KM, Orpen AG, Pringle PG (2003) Chem Commun 2003:278

  41. Pearson RG (1973) Inorg Chem 12:712

    Article  CAS  Google Scholar 

  42. Herebian D, Bothe E, Bill E, Weyhermüller T, Wieghardt K (2001) J Am Chem Soc 123:10012

    Article  CAS  Google Scholar 

  43. Sokolov FD, Baranov SV, Safin DA, Hahn FE, Kubiak M, Pape T, Babahkina MG, Zabirov NG, Galezowska J, Kozlowski H, Cherkasov RA (2007) New J Chem 31:1661

    Article  CAS  Google Scholar 

  44. Tarafder MTH, Islam MAAAA, Howlader MBH, Guidolin N, Zangrando E (2010) Acta Cryst C66:m363

    Google Scholar 

  45. Tampouris K, Coco S, Yannopoulos A, Koinis S (2007) Polyhedron 26:4269

    Article  CAS  Google Scholar 

  46. Duan C-Y, Tian Y-P, Liu Z-H, You X-Y, Mak TCW (1998) J Organomet Chem 570:155

    Article  CAS  Google Scholar 

  47. Glowiak T, Ciszewska T (1982) Acta Cryst B38:1735

    CAS  Google Scholar 

  48. Ali MA, Mirza AH, Butcher RJ, Tarafder MTH, Keat TB, Ali AM (2002) J Inorg Biochem 92:141

    Article  Google Scholar 

  49. Zhou H-P, Li D-M, Wang P, Cheng L-H, Gao Y-H, Zhu Y-M, Wu J-Y, Tian Y-P, Tao X-T, Jiang M-H, Fun H-K (2007) J Mol Struct 826:205

    Article  CAS  Google Scholar 

  50. Chakrabarty K, Kar T, Gupta SPS (1990) Acta Cryst C46:2065

    CAS  Google Scholar 

  51. Martin EM, Bereman RD, Reibenspies J (1992) Inorg Chim Acta 191:171

    Article  CAS  Google Scholar 

  52. Yoda R, Yamamoto Y, Matsushima M, Fujie T, Iitaka Y (1985) Chem Pharm Bull 33:4935

    Article  CAS  Google Scholar 

  53. Matsmoto K, Fukutomi I, Kinoshita I, Oii S (1989) Inorg Chim Acta 158:201

    Article  Google Scholar 

  54. Dessey G, Fares V (1980) Acta Cryst B36:2266

    Google Scholar 

  55. Raj SSR, Fun H-K, Zhu X-H, Chen X-F, You X-Z (2000) Acta Cryst C56:e6

    CAS  Google Scholar 

  56. Fares V, Giuliani AM, Imperatori P, Suber L, Tarli F (1987) J Chem Soc Dalton Trans 1035

  57. Bonamico M, Fares V, Imperatori P, Suber L, Tarli F (1990) J Chem Soc Dalton Trans 931

  58. Kawamoto T, Nagasawa I, Kuma H, Kushi Y (1997) Inorg Chim Acta 265:163

    Article  CAS  Google Scholar 

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Acknowledgments

MGR acknowledges financial support from the Robert A. Welch Foundation (Grant B-1093) and the NSF (CHE-0741936). Prof. Michael B. Hall (TAMU) is thanked for providing us a copy of his JIMP2 program, which was used to prepare the geometry-optimized structures reported here.

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Authors and Affiliations

  1. Department of Chemistry, College of Science, University of Tikrit, Tikrit, Iraq

    Subhi A. Al-Jibori & Noor A. Dayaaf

  2. Department of Chemistry, College of Education for Women, University of Tikrit, Tikrit, Iraq

    Modher Y. Mohammed

  3. Institut für Chemie, Martin-Luther-Universität, Halle-Wittenberg, Kurt-Mothes-Str. 2, 06120, Halle, Germany

    Kurt Merzweiler & Christoph Wagner

  4. Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, UK

    Graeme Hogarth

  5. Department of Chemistry, 1155 Union Circle, Box 305070, Denton, TX, 76203, USA

    Michael G. Richmond

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  1. Subhi A. Al-Jibori
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Correspondence to Graeme Hogarth.

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Al-Jibori, S.A., Dayaaf, N.A., Mohammed, M.Y. et al. cis–trans Isomerism at Square-Planar MN2S2 Centers (M = Pd, Pt): Crystal Structures of N-Phenyl-N-(2-thiazoyl)thiourea Complexes trans-Pd(S2N3C10H8)2 and cis-Pt(S2N3C10H8)2 and Density Functional Calculations. J Chem Crystallogr 43, 365–372 (2013). https://doi.org/10.1007/s10870-013-0429-7

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