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DOI: 10.1039/A702291C (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 2645-2652

Crystal structures, electronic properties and structural pathways of four [Cu(phen)2Cl][Y] complexes (phen = 1,10-phenanthroline; Y = BF4-·0.5H2 O, PF6-, CF3SO3-·H2O or BPh4-)[hair space]

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Gillian Murphy, Pat Nagle, Brian Murphy and Brian Hathaway

Abstract

The crystal structures of [Cu(phen)2Cl][BF4]·0.5H2O 1 (phen = 1,10-phenanthroline), [Cu(phen)2Cl][PF6] 2, [Cu(phen)2Cl][CF3SO3]·H2 O 3 and [Cu(phen)2Cl][BPh4] 4 have been determined by X-ray crystallography. Three of the complexes, 1–3, involve a CuN4Cl chromophore with a square based pyramidal distorted trigonal bipyramidal stereochemistry, while 4 involves a trigonal bipyramidal distorted square based pyramidal stereochemistry. The geometries of the CuN4Cl chromophores in 1–4 were compared by scatter-plot analysis with those of four other [Cu(phen)2Cl][Y] complexes of known structure. The scatter plots of the eight cation distortion isomers of the [Cu(phen)2Cl][Y] complex suggest that all the complexes involve a -A + B route distortion of the CuN4Cl chromophore, -A (ca. 60%) and +B (ca. 40%), The observation of linear and parallel correlations are alternatively interpreted as a direct observation of vibronic coupling of a mixture of the symmetric, νsym, C2 mode and the asymmetric, νasym, non-C2 mode of vibration of the CuN4Cl chromophore. This emphasises the need to determine the structure of more than one complex in a series of cation distortion isomers, in which the limits of the range of stereochemistries are indicated by the measurement of the electronic reflectance spectra.

References

  1. Part 1, W. D. Harrison, D. M. Kennedy, M. Power, R. Sheahan and B. J. Hathaway, J. Chem. Soc., Dalton Trans., 1981, 1556 Search PubMed Part 2, P. Nagle, E. O'Sullivan, B. J. Hathaway and E. Muller, J. Chem. Soc., Dalton Trans., 1990, 3399 RSC.
  2. H. Burgi and J. D. Dunitz, Acc. Chem. Res., 1983, 16, 153 CrossRef; J. D. Dunitz, X-Ray Analysis and Structure of Organic Molecules, Cornell University Press, London, 1979, ch. 7 Search PubMed.
  3. B. J. Hathaway, Struct. Bonding (Berlin), 1984, 57, 55 CAS.
  4. D. Boys, C. Escobar and S. Martinez-Carrera, Acta Crystallogr., Sect. B, 1981, 37, 351 CrossRef.
  5. A. K. Chilkevich, B. P. Ponomarev, P. P. Lyavrentjeu and L. O. Atoumjan, Koord. Khim., 1987, 13, 1532 Search PubMed.
  6. D. Boys, Acta Crystallogr., Sect. C, 1988, 44, 1539 CrossRef.
  7. D. T. Cromer and J. T. Waber, International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4, pp. 71, 148(Present distributor, Kluwer Academic Publishers, Dordrecht) Search PubMed.
  8. G. M. Sheldrick, SHELX 76, program for X-ray crystal structure determination, University of Cambridge, 1976.
  9. G. M. Sheldrick, SHELXS 86, program for X-ray crystal structure solution, University of Göttingen, 1986.
  10. P. Roberts and G. M. Sheldrick, XANADU, program for the calculation of crystallographic data, University of Cambridge, 1979.
  11. K. Henrick, PUBTAB, program to prepare and print crystallographic tables for publication, University of North London, 1980.
  12. P. McCardle, XCAD, program for data reduction of CAD4 output, University College Galway, 1990.
  13. A. L. Spek, PLUTON 92, program to prepare and print molecular structures, University of Utrecht, 1992.
  14. I. M. Procter, B. J. Hathaway and P. Nicholls, J. Chem. Soc. A, 1968, 1678 RSC.
  15. A. W. Addison, T. Nageswara Rao, J. Reedjik, J. van Rijn and G. C. Verschoor, J. Chem. Soc., Dalton Trans., 1984, 1349 RSC.
  16. F. Huq and A. C. Shapski, J. Chem. Soc. A, 1971, 1927 RSC.
  17. G. Murphy, M. Brophy, B. Murphy, C. O'Sullivan and B. J. Hathaway, Acta Crystallogr., Sect. C, 1997, submitted for publication Search PubMed.
  18. G. Murphy, C. Murphy, B. Murphy and B. Hathaway, following paper.
  19. D. Reinen and M. Atanasov, J. Chem. Phys., 1989, 136, 27 CrossRef CAS; Magn. Reson. Rev., 1991, 15, 167 Search PubMed.
  20. M. Bacci, J. Chem. Phys., 1986, 104, 191 CrossRef CAS.
  21. P. Brint, personal communication.
  22. I. B. Bersuker, Coord. Chem. Rev., 1975, 14, 357 CrossRef CAS.
  23. I. B. Bersuker, The Jahn–Teller Effect and Vibronic Interations in Modern Chemistry, Plenum, New York, 1983 Search PubMed.
  24. D. Reinen, Comments Inorg. Chem., 1983, 2, 227 CAS.
  25. D. Reinen, in Vibronic Processes in Inorganic Chemistry, ed. C. D. Flint, Kluwer, Dordrecht, 1989 Search PubMed.
  26. K. Nakamoto, Infrared Spectra of Inorganic and Coordination Compounds, 3rd edn, Wiley, New York, 1978 Search PubMed.
  27. J. Gazo, I. B. Bersuker, J. Garaj, M. Kabesova, J. Kohout, H. Langfeldorova, M. Melnik, M. Serator and F. Valach, Coord. Chem. Rev., 1976, 21, 253 CrossRef CAS.
  28. N. J. Ray, L. Hulett, R. Sheahan and B. J. Hathaway, J. Chem. Soc., Dalton Trans., 1981, 1463 RSC.
  29. E. L. Muetterties and L. T. Guggenberger, J. Am. Chem. Soc., 1974, 96, 1748 CrossRef.
  30. R. R. Holmes and J. A. Deiters, J. Am. Chem. Soc., 1977, 99, 3318 CrossRef CAS.
  31. T. P. Auf der Heyde and H.-B. Burgi, J. Am. Chem. Soc, 1989, 28, 3960, 3970, 3982.
  32. B. J. Hathaway and D. E. Billing, Coord. Chem. Rev., 1970, 5, 143 CrossRef CAS.
  33. B. J. Hathaway, J. Chem. Soc., Dalton Trans., 1972, 1192 RSC.
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