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DOI: 10.1039/A907740E (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 4269-4276

Dimetallic complexes derived from a novel dinucleating chelating symmetric triazole ligand; crystal structure, magnetic properties and ESR study of bis[µ-3,5-diacetylamino-1,2,4-triazolato-O[hair space]′,N[hair space] 1,N[hair space] 2,O[hair space]″]bis[(nitrato)(aqua)copper(II)][hair space]‡

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Sacramento Ferrer, Petra J. van Koningsbruggen, Jaap G. Haasnoot, Jan Reedijk, Huub Kooijman, Anthony L. Spek, Luis Lezama, Atta M. Arif and Joel S. Miller

Abstract

Reaction of 3,5-diacetylamino-1,2,4-triazole (Hdaat) with copper(II), nickel(II) and cobalt(II) salts yields dinuclear co-ordination compounds, which were spectroscopically characterized. The crystal and molecular structure of one of the compounds, bis[µ-3,5-diacetylamino-1,2,4-triazolato-O[hair space]′,N[hair space] 1,N[hair space] 2,O[hair space]″]bis[(nitrato)(aqua)copper(II)] 1, was determined by single-crystal X-ray diffraction. Complex 1 consists of dinuclear units with an inversion center at the midpoint of the Cu–Cu vector. The most remarkable feature of this structure is that the daat ligand forms a six-membered chelate ring [Cu–N3–C3–N1–C2–O1; Cua–N4–C4–N5–C5–O2], in contrast with the five-membered chelate rings always found in comparable triazole derived dimers. This structural feature is studied in the context of the geometry of the bridging system. Variable-temperature ESR spectral and magnetic susceptibility data indicate antiferromagnetic behaviour. The magnetic susceptibility data (4–290 K) are interpreted using the spin Hamiltonian Ĥ = –2J(ŜCu1·ŜCu2), and yielded J = –36 cm–1 and g = 2.13. The magnitude of the exchange interaction is compared with previously reported magnetostructural data for related double 1,2,4-triazole-N[hair space]1,N[hair space]2 bridged dinuclear copper(II) compounds. A correlation between the exchange parameter J and the N–Cu–N angle is described. Variable-temperature magnetic susceptibility measurements (2–300 K) for the Ni(II) and Co(II) analogous compounds confirmed the dimeric nature of these compounds and showed the presence of antiferromagnetic exchange; the corresponding J values are rationalized on the basis of the structural features of the isostructural Cu(II) compound 1.

References

  1. D. Gatteschi, O. Kahn, J. S. Miller and F. Palacio(Editors), Magnetic Molecular Materials, Kluwer Academic, Dordrecht, 1991 Search PubMed; O. Kahn, Y. Pei and Y. Yournaux, in Inorganic Materials, eds. D. W. Bruce and D. O'Hare, John Wiley & Sons, Chichester, 1992 Search PubMed; O. Kahn, Molecular Magnetism, VCH Publishers, New York, 1993 Search PubMed; M. M. Turnbull, T. Sugimoto and L. K. Thompson(Editor), Molecule-Based Magnetic Materials: Theory, Techniques, and Applications, ACS Symp. Ser., Washington, DC, 1996, 644 Search PubMed.
  2. A. Escuer, R. Vicente, J. Ribas, M. S. E. Fallah, X. Solans and M. Font-Bardia, Inorg. Chem., 1993, 22, 3727 CrossRef.
  3. (a) K. K. Nanda, L. K. Thompson, J. N. Bridson and K. Nag, J. Chem. Soc., Chem. Commun., 1994, 1337 RSC; (b) Z. Xu, L. K. Thompson and D. O. Miller, Inorg. Chem., 1997, 36, 3985 CrossRef CAS.
  4. E. Ruiz, P. Alemany, S. Alvarez and J. Cano, Inorg. Chem., 1997, 36, 3683 CrossRef CAS.
  5. V. H. Crawford, H. W. Richardson, J. R. Wasson, D. J. Hodgson and W. E. Hatfield, Inorg. Chem., 1976, 15, 2107 CrossRef.
  6. B. Mernari, F. Abraham, M. Lagrenee, M. Drillon and P. Legoll, J. Chem. Soc., Dalton Trans., 1993, 1707 RSC.
  7. R. Prins, P. J. Birker, J. G. Haasnoot, G. C. Verschoor and J. Reedijk, Inorg. Chem., 1985, 24, 4128 CrossRef CAS.
  8. W. M. E. Koomen-van Oudenniel, R. A. G. de Graaff, J. G. Haasnoot, R. Prins and J. Reedijk, Inorg. Chem., 1989, 28, 1128 CrossRef CAS.
  9. P. J. van Koningsbruggen, J. G. Haasnoot, R. A. G. de Graaff, J. Reedijk and S. Slingerland, Acta Crystallogr., Sect. C, 1992, 48, 1923 CrossRef.
  10. P. M. Slangen, P. J. van Koningsbruggen, J. G. Haasnoot, J. Jansen, S. Gorter, J. Reedijk, H. Kooijman, W. J. J. Smeets and A. L. Spek, Inorg. Chim. Acta, 1993, 212, 289 CrossRef CAS.
  11. P. M. Slangen, P. J. van Koningsbruggen, K. Goubitz, J. G. Haasnoot and J. Reedijk, Inorg. Chem., 1994, 33, 1121 CrossRef.
  12. F. B. Hulsbergen, R. W. M. ten Hoedt, G. C. Verschoor, J. Reedijk and A. L. Spek, J. Chem. Soc., Dalton Trans., 1983, 539 RSC; R. W. M. ten Hoedt, F. B. Hulsbergen, G. C. Verschoor and J. Reedijk, Inorg. Chem., 1982, 21, 2369 CrossRef.
  13. D. Ajò, A. Bencini and Fabrizio Mani, Inorg. Chem., 1988, 27, 2437 CrossRef CAS.
  14. M. G. B. Drew, P. C. Yates, F. S. Esho, J. Trocha-Grimshaw, A. Lavery, K. P. McKillop, S. M. Nelson and J. Nelson, J. Chem. Soc., Dalton Trans., 1988, 2995 RSC.
  15. J. Casabó, J. Pons, K. S. Siddiqi, F. Teixidor, E. Molins and C. Miravitlles, J. Chem. Soc., Dalton Trans., 1989, 1401 RSC.
  16. T. Kamiusuki, H. Okawa, M. Matsumoto and S. Kida, J. Chem. Soc., Dalton Trans., 1989, 2077 RSC; T. Kamiusuki, H. Okawa, M. Matsumoto and S. Kida, J. Chem. Soc., Dalton Trans., 1990, 195 RSC.
  17. J. C. Bayón, P. Esteban, G. Net, P. G. Rasmussen, K. N. Baker, C. W. Hahn and M. M. Gumz, Inorg. Chem., 1991, 30, 2572 CrossRef CAS.
  18. V. P. Hanot, T. D. Robert, J. Kolnaar, J. G. Haasnoot, J. Reedijk, H. Kooijman and A. L. Spek, J. Chem. Soc., Dalton Trans., 1996, 4275 RSC.
  19. T. C. Woon, R. McDonald, S. K. Mandal, L. K. Thompson, S. P. Connors and A. W. Addison, J. Chem. Soc., Dalton Trans., 1986, 2381 RSC.
  20. L. K. Thompson, F. L. Lee and E. J. Gabe, Inorg. Chem., 1988, 27, 39 CrossRef CAS.
  21. S. S. Tandon, L. K. Thompson and R. C. Hynes, Inorg. Chem., 1992, 31, 2210 CrossRef CAS.
  22. L. Banci, A. Bencini, C. Benelli and D. Gatteschi, Inorg. Chem., 1982, 21, 3868 CrossRef CAS.
  23. L. Rosenberg, L. K. Thompson, E. J. Gabe and F. L. Lee, J. Chem. Soc., Dalton Trans., 1986, 625 RSC; S. K. Mandal, L. K. Thompson, E. J. Gabe, J. P. Charland and F. L. Lee, Inorg. Chem., 1988, 27, 855 CrossRef CAS.
  24. F. Abraham, M. Lagrenee, S. Sueur, B. Mernari and C. Bremard, J. Chem. Soc., Dalton Trans., 1991, 1443 RSC.
  25. S. Ferrer, J. Borrás, C. Miratvitlles and A. Fuertes, Inorg. Chem., 1990, 29, 206 CrossRef CAS.
  26. J. C. Pedregosa, J. Casanova, G. Alzuet, J. Borrás, S. García-Granda, M. R. Díaz and A. Gutiérrez-Rodríguez, Inorg. Chim. Acta, 1995, 232, 117 CrossRef CAS.
  27. P. J. van Koningsbruggen, E. Müller, J. G. Haasnoot and J. Reedijk, Inorg. Chim. Acta, 1993, 208, 37 CrossRef CAS.
  28. A. Bencini, D. Gatteschi, C. Zanchini, J. G. Haasnoot, R. Prins and J. Reedijk, Inorg. Chem., 1985, 24, 2812 CrossRef CAS.
  29. B. G. van den Bos, Recl. Trav. Chim. Pays-Bas, 1960, 79, 836 CAS.
  30. J. A. Nelder and R. Mead, Comput. J., 1965, 7, 308 Search PubMed.
  31. A. J. M. Duisenberg, Acta Crystallogr., Sect. A, 1983, 39, 211 CrossRef.
  32. P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, S. García-Granda, R. O. Gould, J. M. M. Smits and C. Smykalla, The DIRDIF program system, Technical report of the Crystallography Laboratory, University of Nijmegen, 1992.
  33. G. M. Sheldrick, SHELX76, Program for Crystal Structure Determination, University of Cambridge, 1976.
  34. A. L. Spek, Acta Crystallogr., Sect. A, 1990, 46, C34.
  35. P. J. van Koningsbruggen, J. W. van Hal, R. A. G. de Graaff, J. G. Haasnoot and J. Reedijk, J. Chem. Soc., Dalton Trans., 1993, 2163 RSC.
  36. P. J. van Koningsbruggen, J. W. van Hal, E. Müller, R. A. G. de Graaff, J. G. Haasnoot and J. Reedijk, J. Chem. Soc., Dalton Trans., 1993, 1371 RSC.
  37. W. Vreugdenhil, Ph. D. Thesis, Leiden University, 1987.
  38. S. Ferrer, J. G. Haasnoot, J. Reedijk, E. Müller, M. Biagini Cingi, M. Lanfranchi, A. M. Manotti Lanfredi and J. Ribas, Inorg. Chem., submitted Search PubMed.
  39. B. Bleaney and K. D. Bowers, Proc. R. London, A, 1952, 214, 451 Search PubMed.
  40. A. P. Ginsberg, Inorg. Chem., 1972, 11, 2884 CrossRef CAS.
  41. V. T. Kalinnikov, Y. V. Ratikin and W. E. Hatfield, Inorg. Chim. Acta, 1978, 31, 1 CrossRef CAS.
  42. L. J. de Jongh and A. R. Miedema, Adv. Phys., 1974, 23, 1 CAS.
  43. J. C. Bonner and M. E. Fisher, Phys. Rev. A, 1964, 135, 640.
  44. M. E. Fisher, J. Math. Phys. (N.Y.), 1963, 4, 124 Search PubMed.
  45. P. J. van Koningsbruggen, M. W. Gluth, V. Ksenofontov, D. Walcher, D. Schollmeyer, G. Levchenko and P. Gütlich, Inorg. Chim. Acta, 1998, 273, 54 CrossRef CAS.
  46. F. S. Keij, R. A. G. de Graaff, J. G. Haasnoot and J. Reedijk, J. Chem. Soc., Dalton Trans., 1984, 2093 RSC.
  47. B. Cabezón, A. Sastre, T. Torres, W. Schäfer, J. J. Borrás-Almenar and E. Coronado, J. Chem. Soc., Dalton Trans., 1995, 2305 RSC.
  48. P. D. W. Boyd, A. D. Toy, T. D. Smith and J. R. Pilbrow, J. Chem. Soc., Dalton Trans., 1973, 1549 RSC; C. Delfs and R. Bramley, J. Chem. Soc., Dalton Trans., 1998, 1191 RSC.
  49. B. J. Hathaway and D. E. Billing, Coord. Chem. Rev., 1970, 5, 143 CrossRef CAS.
  50. P. J. van Koningsbruggen, D. Gatteschi, R. A. G. de Graaff, J. G. Haasnoot, J. Reedijk and C. Zanchini, Inorg. Chem., 1995, 34, 5175 CrossRef CAS.
  51. J. Reedijk, D. Knetsch and B. Nieuwenhuisje, Inorg. Chim. Acta, 1971, 5, 568 CrossRef CAS.
  52. K. Nonoyama, H. Ojima and M. Nonoyama, Inorg. Chim. Acta, 1984, 84, 13 CrossRef CAS.
  53. A. B. P. Lever, Inorganic Electronic Spectroscopy, Elsevier, Amsterdam, 2nd edn., 1984 Search PubMed.
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