Crystal structures, electronic properties and structural pathways of two [Cu(phen)₂(OH₂)][Y]₂ complexes (phen = 1,10-phenanthroline, Y = CF₃SO₃^- or ClO₄^-) 

Abstract

The crystal structures of [Cu(phen)₂(OH₂)][CF₃SO₃] ₂ 1 and [Cu(phen)₂(OH₂)][ClO₄]₂ 2 (phen = 1,10-phenanthroline) have been determined by diffractometer data collection. The CuN₄O chromophores in both complexes 1 and 2 lie on a crystallographic two-fold axis, with a square pyramidal distorted trigonal bipyramidal stereochemistry, an elongation along the Cu–O direction, Cu–O 2.066(3) and 2.245(4) Å, and an increase in the N(4)–Cu–N(2) α₃ angle to 123.4(1) and 136.0(1)°, respectively. This suggests that the stereochemistry of 1 is best described as near regular trigonal bipyramidal, RTB, and that of 2 as square based pyramidal distorted trigonal bipyramidal, SBPDTB. The structures of 1 and 2 were compared by scatter-plot analysis, with other [Cu(chelate ligand)₂(OH₂)][Y]₂ complexes involving two-fold axes of symmetry. This shows that the spread of the data points is not random, is relatively large and suggests the presence of vibronic coupling to account for the distortion from the RTB CuN₄O chromophore, along the C₂ dominated +A and -A route distortions. A continuous linear structural pathway is suggested, determined by the coupled ν_sym^str and ν_sym^bend modes of vibration, involving a progression of 40–50 modes, spanning an angular distortion range of 91–140°, which correlate with electronic and ESR spectral data.

References

1. Part 3, G. Murphy, P. Nagle, B. Murphy and B. J. Hathaway, preceding paper.
2. H. Burgi and J. D. Dunitz, Acc. Chem. Res., 1983, 16, 153; J. D. Dunitz, X-Ray Analysis and Structure of Organic Molecules, Cornell University Press, London, 1979, ch. 7.
3. B. J. Hathaway, Struct. Bonding (Berlin), 1984, 57, 55.
4. W. D. Harrison, D. M. Kennedy, N. J. Ray, R. Sheahan and B. J. Hathaway, J. Chem. Soc., Dalton Trans., 1981, 1556.
5. P. Nagle, E. O'Sullivan, B. J. Hathaway and E. Muller, J. Chem. Soc., Dalton Trans., 1990, 3399.
6. E. Muller, C. Piguet, G. Berandinelli and A. F. Williams, Inorg. Chem., 1988, 27, 849.
7. E. Muller, FACAN, program for factor analysis, written in Turbo Pascal (IBM and compatible), 1989.
8. E. R. Malinowski and D. G. Howery, Factor Analysis in Chemistry, Wiley, New York, 1980.
9. D. Cunningham, Ph.D. Thesis, National University of Ireland, 1992.
10. A. W. Addison, T. Nageswara Rao, J. Reedjik, J. van Rijn and G. C. Verschoor, J. Chem. Soc., Dalton Trans., 1984, 1349.
11. M. Liu and S. K. Arora, Acta Crystallogr., Sect. C, 1993, 49, 373.
12. H. Nakai and Y. Deguchi, Bull. Chem. Soc. Jpn., 1975, 48, 2557.
13. H. Nakai and Y. Noda, Bull. Chem. Soc. Jpn., 1978, 51, 1386.
14. P. McCardle, XCAD, program for data reduction of CAD4 output, University College Galway, 1990.
15. G. M. Sheldrick, SHELX 76, program for X-ray crystal structure determination, University of Cambridge, 1976.
16. G. M. Sheldrick, SHELXS 86, program for X-ray crystal structure solution, University of Göttingen, 1986.
17. 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, Dordrecht).
18. P. Roberts and G. M. Sheldrick, XANADU, program for the calculation of crystallographic data, University of Cambridge, 1979.
19. K. Henrick, PUBTAB, program to prepare and print crystallographic tables for publication, Polytechnic of North London, 1980.
20. A. L. Spek, PLUTON 92, graphics program to prepare and print molecular structures, University of Utrecht, 1992.
21. F. Huq and A. C. Shapski, J. Chem. Soc. A, 1971, 1927.
22. R. J. Fereday, P. Hodgson, S. Tyagi and B. J. Hathaway, J. Chem. Soc., Dalton Trans., 1981, 2070.
23. W. D. Harrison and B. J. Hathaway, Acta Crystallogr., Sect. B, 1980, 36, 1069.
24. W. D. Harrison and B. J. Hathaway, Acta Crystallogr., Sect. B, 1979, 35, 2910.
25. L. W. Morgan, W. T. Pennington, J. D. Petersen, R. R. Ruminski, D. W. Bennett and J. S. Rommel, Acta Crystallogr., Sect. C, 1992, 48, 163.
26. G. De Munno, G. Bruno, M. Julve and M. Romeo, Acta Crystallogr., Sect. C, 1990, 46, 1828.
27. W. D. Harrison, B. J. Hathaway and D. Kennedy, Acta Crystallogr., Sect. B, 1979, 35, 2301.
28. N. Ray, L. Hulett, R. Sheahan and B. J. Hathaway, J. Chem. Soc., Dalton Trans., 1981, 1463.
29. O. J. Parker, G. T. Greiner, G. L. Breneman and R. D. Willett, Polyhedron, 1994, 2, 267.
30. C. Harrington and B. J. Hathaway, unpublished work.
31. T. W. Hambley, C. L. Raston and A. H. White, Aust. J. Chem., 1977, 30, 1965.
32. P. Brint, personal communication.
33. I. B. Bersuker, Coord. Chem. Rev., 1975, 14, 357.
34. I. B. Bersuker, The Jahn–Teller Effect and Vibronic Interactions in Modern Chemistry, Plenum, New York, 1983.
35. D. Reinen, Comments Inorg. Chem, 1983, 2, 227; D. Reinen and M. Atanasov, J. Chem. Phys., 1989, 136, 27; Magn. Reson. Rev. 1991, 15, 167.
36. A. F. Cameron, D. W. Taylor and R. H. Nuttall, J. Chem. Soc., Dalton Trans., 1972, 1603; R. J. Dudley, B. J. Hathaway, P. G. Hodgson, P. C. Power and D. J. Loose, J. Chem. Soc., Dalton Trans., 1974, 1005.
37. M. J. Arriortua, J. L. Mesa, T. Rojo, T. Debaerdemaeker, D. Beltran-Porter, H. Stratemeier and D. Reinen, Inorg. Chem., 1988, 27, 2976.
38. J. Pinkas, J. C. Huffman, M. H. Chisholm and K. G. Caulton, Inorg. Chem., 1995, 34, 5314.
39. L. Funk and T. R. Ortolano, Inorg. Chem., 1968, 7, 567; J. Pinkas, J. C. Huffman, D. V. Baxter and M. H. Chisholm, Chem. Mater., 1995, 7, 1589.
40. B. J. Hathaway and D. E. Billing, Coord. Chem. Rev., 1970, 5, 143.
41. B. J. Hathaway, Comprehensive Coordination Chemistry. The Synthesis, Reactions, Properties and Applications of Coordination Compounds, eds. G. Wilkinson, R. D. Gillard and J. A. McCleverty, Pergamon, Oxford, 1988, vol. 5, pp. 533–774.
42. S. Tyagi, B. J. Hathaway, S. Kremer, H. Stratemeier and D. Reinen, J. Chem. Soc., Dalton Trans., 1984, 2087.
43. J. Foley, D. Kennefick, S. Tyagi and B. J. Hathaway, J. Chem. Soc., Dalton Trans., 1983, 2333; H. Nakai, Bull. Chem. Soc. Jpn., 1971, 44, 2412.
44. B. J. Hathaway, J. Chem. Soc., Dalton Trans., 1972, 1196.
45. K. L. Bray and H. G. Drickamer, J. Phys. Chem., 1989, 93, 7604; H. C. Drickamer and K. L. Bray, Acc. Chem. Res., 1990, 23, 55.
46. A. A. G. Tomlinson and B. J. Hathaway, Coord. Chem., 1970, 5, 1.