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DOI: 10.1039/A804990D (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 3125-3132

Influence of the counterion on the coordinating properties of (2,2′-bipyridyl)bis(oxalato)chromate(III) anion: crystal structures and magnetic properties of AsPh4[Cr(bipy)(ox)2]·H2O and [NaCr(bipy)(ox)2(H2O)]·2H2O

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M. Carmen Muñoz, Miguel Julve, Francesc Lloret, Juan Faus and Marius Andruh

Abstract

Two new chromium(III)-containing complexes of formula AsPh4[Cr(bipy)(ox)2]·H2O 1 and [NaCr(bipy)(ox)2(H2O)]· 2H2O 2 (bipy = 2,2′-bipyridine and ox = oxalate dianion) have been synthesized and characterized by single-crystal X-ray diffraction. The structure of 1 consists of discrete [Cr(bipy)(ox)2]– mononuclear anions, tetraphenylarsonium cations and uncoordinated water molecules. The structure of 2 reveals a novel two-dimensional framework which is made up of oxalato-bridged bimetallic CrIII–NaI helical chains which are interconnected through centrosymmetric Na2O2 units. Within the chain, a regular alternation of the metal ions is observed, the oxalate group acting as a bis(chelating) ligand. In addition to this coordination mode, two oxalates each act as monodentate ligands towards a sodium atom of a neighbouring chain thus leading to a sheetlike polymeric structure. The chromium environment is distorted octahedral in both complexes: two nitrogen atoms from a bidentate bipy ligand and four oxygen atoms from either two chelating (1) or two bis(chelating) (2) oxalate groups build the coordination polyhedron around the chromium atom. The Cr–N bond lengths [values in the ranges 2.077(3)–2.057(3) (1) and 2.067(4)–2.058(4) Å (2)] are somewhat longer than the Cr–O ones [values in the ranges 1.960(2)–1.946(2) (1) and 1.968(3)–1.949(3) Å (2)]. The sodium atom in 2 is also six-coordinated: a coordinated water molecule [2.371(5) and 2.325(4) Å for Na(1)–O(17) and Na(2)–O(18), respectively] and five oxygens from three oxalate groups [values of the Na–O (ox) bonds in the ranges 2.511(4)–2.331(4) and 2.481(4)–2.364(4) Å around Na(1) and Na(2), respectively] build a distorted octahedral NaO6 environment. The intralayer chromium–sodium and sodium–sodium distances through bridging oxalate in 2 vary in the ranges 5.657(4)–5.579(2) and 3.534(3)–3.497(4) Å, respectively. Variable-temperature magnetic susceptibility measurements of 1 and 2 reveal the occurrence of very weak antiferromagnetic interactions together with zero-field splitting effects in both compounds. The use of the [Cr(bipy)(ox)2]– unit as a ligand towards different univalent and divalent metal ions aimed at designing new heterobimetallic systems is analysed and discussed in the light of available structural data.

References

  1. T. R. Felthouse, E. J. Laskowski and D. N. Hendrickson, Inorg. Chem., 1977, 16, 1077 CrossRef CAS.
  2. M. Julve, M. Verdaguer, A. Gleizes, M. Philoche-Levisalles and O. Kahn, Inorg. Chem., 1983, 22, 3808.
  3. M. F. Charlot, M. Verdaguer, Y. Journaux, P. de Loth and J. P. Daudey, Inorg. Chem., 1984, 23, 3802 CrossRef CAS.
  4. M. Verdaguer, O. Kahn, M. Julve and A. Gleizes, Nouv. J. Chim., 1985, 9, 325 Search PubMed.
  5. A. Bencini, A. C. Fabretti, C. Zanchini and P. Zannini, Inorg. Chem., 1987, 26, 1445 CrossRef CAS.
  6. L. Soto, J. García, E. Escrivá, J. P. Legros, J. P. Tuchagues, F. Dahan and A. Fuertes, Inorg. Chem., 1989, 28, 3378 CrossRef CAS.
  7. S. Alvarez, M. Julve and M. Verdaguer, Inorg. Chem., 1990, 29, 4500 CrossRef CAS.
  8. A. Gleizes, M. Julve, M. Verdaguer, J. A. Real, J. Faus and X. Solans, J. Chem. Soc., Dalton Trans., 1992, 3209 RSC.
  9. J. Glerup, P. A. Goodson, D. J. Hodgson and K. Michelsen, Inorg. Chem., 1995, 34, 6255 CrossRef CAS.
  10. P. Román, C. Guzmán-Miralles, A. Luque, J. I. Beitia, J. Cano, F. Lloret, M. Julve and S. Alvarez, Inorg. Chem., 1996, 35, 3741 CrossRef CAS and refs. therein.
  11. I. Muga, J. M. Gutiérrez-Zorrilla, A. Luque, P. Román and F. Lloret, Inorg. Chem., 1997, 36, 743 CrossRef CAS.
  12. M. Ohba, H. Tamaki, N. Matsumoto and H. Okawa, Inorg. Chem., 1993, 32, 5385 CrossRef CAS.
  13. Y. Pei, Y. Journaux and O. Kahn, Inorg. Chem., 1989, 28, 100 CrossRef CAS.
  14. H. Tamaki, Z. J. Zhong, N. Matsumoto, S. Kida, M. Koikawa, N. Achiwa, Y. Hashimoto and H. Okawa, J. Am. Chem. Soc., 1992, 114, 6974 CrossRef.
  15. L. O. Atovmian, G. V. Shilov, R. N. Lyubokskaya, E. I. Zhilyaeva, N. S. Ovanesyan, S. I. Pirumova, I. G. Gusakovskaya and Y. G. Morozov, JETP Lett. (Engl. Transl.), 1993, 58, 766 Search PubMed.
  16. S. Decurtins, H. W. Schmalle, H. R. Oswald, A. Linden, J. Ensling, P. Gütlich and A. Hauser, Inorg. Chim. Acta, 1994, 216, 65 CrossRef CAS.
  17. S. G. Carling, C. Mathonière, P. Day, K. M. Abdul Malik, S. J. Coles and M. B. Hursthouse, J. Chem. Soc., Dalton Trans., 1996, 1839 RSC; C. Mathonière, C. J. Nuttall, S. G. Carling and P. Day, Inorg. Chem., 1996, 35, 1201 CrossRef CAS.
  18. R. Pellaux, H. W. Schmalle, R. Huber, P. Fisher, T. Hauss, B. Ouladdiaf and S. Decurtins, Inorg. Chem., 1997, 36, 2301 CrossRef CAS.
  19. S. Decurtins, H. W. Schmalle, P. Schneuwly, J. Ensling and P. Gütlich, J. Am. Chem. Soc., 1994, 116, 9521 CrossRef CAS.
  20. S. Decurtins, H. W. Schmalle, R. Pellaux, P. Schneuwly and A. Hauser, Inorg. Chem., 1996, 35, 1451 CrossRef CAS.
  21. J. A. Broomhead and F. D. Dwyer, Aust. J. Chem., 1961, 14, 250 CAS.
  22. K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, Wiley, New York, 4th edn., 1986, p. 228 Search PubMed.
  23. A. Earnshaw, Introduction to Magnetochemistry, Academic Press, London, New York, 1968 Search PubMed.
  24. G. M. Sheldrick, SHELXS 86, A Program for Crystal Structure Determination, University of Göttingen, 1986; SHELXL 93, Program for the ReWnement of Crystal Structures, University of Göttingen, 1993.
  25. International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4, p. 99 Search PubMed.
  26. C. K. Johnson, ORTEP, Report ORNL-3794, Oak Ridge National Laboratory, Oak Ridge, TN, 1971.
  27. J. N. van Niekerk and F. R. L. Schoening, Acta Crystallogr., 1952, 5, 196 CrossRef CAS; R. H. Fenn, A. J. Graham and R. D. Guillard, Nature (London), 1967, 213, 1012 CAS; D. Taylor, Aust. J. Chem., 1978, 31, 1455 CAS.
  28. M. Andruh, R. Melanson, C. V. Stager and F. D. Rochon, Inorg. Chim. Acta, 1996, 251, 309 CrossRef CAS.
  29. F. D. Rochon, R. Melanson and M. Andruh, Inorg. Chem., 1996, 35, 6086 CrossRef CAS.
  30. L. L. Merrit and E. D. Schroeder, Acta Crystallogr., 1956, 9, 801 CrossRef.
  31. J. Baldas, S. F. Colmanet and M. F. Mackay, J. Chem. Soc., Dalton Trans., 1988, 1725 RSC; R. Vicente, J. Ribas, S. Alvarez, A. Seguí, X. Solans and M. Verdaguer, Inorg. Chem., 1987, 26, 4004 CrossRef CAS; R. Grenz, F. Götzfried, U. Nagel and W. Beck, Chem. Ber., 1986, 119, 1217 CrossRef CAS.
  32. I. Dance and M. Scudder, J. Chem. Soc., Chem. Commun., 1995, 1039 RSC and refs. therein.
  33. C. J. O'Connor, Prog. Inorg. Chem., 1986, 29, 203.
  34. A. J. Amoroso, J. C. Jeffery, P. L. Jones, J. A. McCleverty, P. Thornton and M. D. Ward, Angew. Chem., Int. Ed. Engl., 1995, 34, 1443 CrossRef CAS.
  35. N. Stanica, C. V. Stager, M. Cimpoesu and M. Andruh, Polyhedron, 1998, 17, 1787 CrossRef CAS.
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