Bis(didentate) open-chain and tetradentate pseudo-macrocyclic bridging co-ordination modes of N,N′ -bis(1,3-dimethyl-5-nitroso-2,4-dioxopyrimidin-6-yl)butane-1,4-diamine

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Enrique Colacio, José M. Domínguez-Vera, Albert Escuer, Raikko Kivekäs, Martti Klinga, José-María Moreno and Antonio Romerosa


Abstract

The reaction of N,N′ -bis(1,3-dimethyl-5-nitroso-2,4-dioxopyrimidin-6-yl)butane-1,4-diamine (H2L2) with copper(II) salts in ethanol yielded mononuclear complexes of formula [Cu(HL2)X] (X is the anion of the corresponding copper salt). These mononuclear precursors reacted with either CuII and 2,2′-bipyridine (bipy) or [NiL][ClO4]2 (L = d,l -5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) to afford the homodinuclear complexes [Cu(µ-Cl)(µ-L2)Cu(bipy)]ClO4·2H 2O 1 and [LNi(µ-H2L2)NiL][ClO4]42, respectively. Within the dinuclear cation of 1 the copper(II) ions exhibit a 4 + 1 co-ordination environment. The dioxime ligand bridges the basal planes of the metal ions through the oximate groups in a symmetrical syn-syn fashion, Cu(1) · · · Cu(2) being 3.364(3) Å, whereas their apical positions are occupied by a bridging Cl anion, with a Cu(1)–Cl(1)–Cu(2) angle of 80.42(7)°. A magnetic study of 1 revealed that the antiferromagnetic exchange is so strong as to cause complete spin pairing at room temperature. Complex 2 consists of a homodinuclear [LNi(µ-H2L2)NiL]4+ cation and four non-co-ordinated perchlorate anions. The ligand adopts an unusual bis(didentate) open-chain co-ordination mode by elimination of the Cu atom occupying the inner site of the pseudo-macrocyclic ligand in the mononuclear precursor. This results in a Ni · · · Ni distance of 13.370(3) Å. The nickel(II) ions are octahedrally co-ordinated by four nitrogen atoms belonging to the macrocyclic ligand L and the N and O atoms from the nitroso and the neighbouring exocyclic group. The co-ordination modes of H2L2 are compared to those of the related N,N′ -bis(1,3-dimethyl-5-nitroso-2,4-dioxopyrimidin-6-yl)propane-1,3-diamine (H2L1).


References

  1. Magneto-Structural Correlations in Exchange Coupled Systems, eds. R. D. Willet, D. Gatteschi and O. Kahn, Reidel, Dordrecht, NATO ASI Ser. C, 1985, vol. 140 Search PubMed.
  2. O. Kahn, Molecular Magnetism, VCH, Weinheim, 1993 Search PubMed.
  3. Magnetic Molecular Materials, eds. D. Gatteschi, O. Kahn, J. S. Miller and F. Palacio, Kluwer, Dordrecht, 1991 Search PubMed.
  4. J. G. Mohanty, S. Baral, R. P. Singh and A. Chakravorty, Inorg. Nucl. Chem. Lett., 1974, 10, 665 Search PubMed; J. A. Bertrand, J. H. Smith and P. G. Eller, Inorg. Chem., 1974, 13, 1649 CrossRef CAS; R. Beckett, R. Colton, B. F. Hoskins, R. L. Martin and D. G. Vince, Aust. J. Chem., 1969, 22, 2527 CAS; R. Beckett and B. F. Hoskins, J. Chem. Soc., Dalton Trans., 1972, 921 Search PubMed; H. Okawa, M. Koikawa, S. Kida, D. Luneau and H. Oshio, J. Chem. Soc., Dalton Trans., 1990, 469 RSC; P. Chaudhuri, M. Winter, B. P. C. Della Vedova, E. Bill, A. Trautwein, S. Ghering, P. Fleischauer, B. Nuber and J. Weiss, Inorg. Chem., 1991, 30, 2148 CrossRef CAS.
  5. D. Luneau, H. Oshio, H. Okawa and S. Kida, J. Chem. Soc., Dalton Trans., 1990, 2283 RSC; D. Luneau, H. Oshio, H. Okawa, M. Koikawa and S. Kida, Bull. Chem. Soc. Jpn., 1990, 63, 2212 CAS; Z. Zhong, H. Okawa, N. Matsumoto, H. Sakiyama and S. Kida, J. Chem. Soc., Dalton Trans., 1991, 497 RSC; R. Ruiz, J. Sanz, B. Cervera, F. Lloret, M. Julve, C. Bois, J. Faus and M. C. Muñoz, J. Chem. Soc., Dalton Trans., 1993, 1623 RSC; F. Lloret, R. Ruiz, M. Julve, J. Faus, Y. Yournaux, I. Castro and M. Verdaguer, Chem. Mater., 1992, 4, 1150 CrossRef CAS; P. Basu, S. Pal and A. Chakravorty, J. Chem. Soc., Dalton Trans., 1991, 3217 RSC; S. Pal, R. Mukherjee, M. Tomas, L. R. Falvello and A. Chakravorty, Inorg. Chem., 1986, 25, 200 CrossRef CAS; R. Ruiz, J. Sanz, F. Lloret, M. Julve, J. Faus, C. Bois and M. C. Muñoz, J. Chem. Soc., Dalton Trans., 1993, 3035 RSC; P. Chaudhuri, M. Winter, P. Fleischauer, W. Haase, U. Florke and J. Haupt, J. Chem. Soc., Chem. Commun., 1990, 1728 RSC; R. Ruiz, F. Lloret, M. Julve, M. C. Muñoz and C. Bois, Inorg. Chim. Acta, 1994, 219, 179 CrossRef CAS.
  6. E. Colacio, J. M. Dominguez-Vera, A. Escuer, M. Klinga, R. Kivekäs and A. Romerosa, J. Chem. Soc., Dalton Trans., 1995, 343 RSC.
  7. (a) E. Colacio, J. M. Dominguez-Vera, A. Escuer, R. Kivekäs and A. Romerosa, Inorg. Chem., 1994, 33, 3914 CrossRef CAS; (b) E. Colacio, J. M. Dominguez-Vera, A. Romerosa, R. Kivekäs, M. Klinga and A. Escuer, Inorg. Chim. Acta, 1995, 234, 61 CrossRef CAS; (c) J. M. Dominguez-Vera, E. Colacio, A. Escuer, M. Klinga, R. Kivekäs and A. Romerosa, Polyhedron, 1997, 281, 16.
  8. H. Funchs, M. Gottlieb and W. Pfleiderer, Chem. Ber., 1978, 111, 982.
  9. N. F. Curtis, D. A. Swann and T. N. Waters, J. Chem. Soc., Dalton Trans., 1973, 1963 RSC.
  10. International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4 (present distributor: Kluwer, Dordrecht) Search PubMed.
  11. G. M. Sheldrick, SHELXS 86, Program for Solution of Crystal Structures, University of Göttingen, 1986.
  12. XTAL3.2 Reference Manual, eds. S. R. Hall, H. D. Flack and J. M. Stewart, Universities of Western Australia and Maryland, 1992 Search PubMed.
  13. E. Colacio, J. M. Dominguez-Vera, J. M. Moreno, A. Romerosa, R. Kivekäs and A. Pajunen, unpublished work.
  14. A. W. Addison, P. J. Burke and H. Henrick, Inorg. Chem., 1982, 21, 60 CrossRef CAS.
  15. (a) J. H. Timmons, J. W. L. Martin, A. E. Martell, P. Rudolf, A. Clearfield and R. C. Buckley, Inorg. Chem., 1981, 20, 3056 CrossRef CAS; (b) W. M. Davis, A. Zask, K. Nakanishi and S. J. Lippard, Inorg. Chem., 1985, 24, 3737 CrossRef CAS; (c) J. Pal, R. K. Murmann, E. O. Schlemper, C. K. Fair and M. S. Hussain, Inorg. Chim. Acta, 1986, 115, 153 CrossRef CAS; (d) J. Müller, K. Felix, C. Maichle, E. Lengfelder, J. Strähle and U. Weser, Inorg. Chim. Acta, 1995, 233, 11 CrossRef.
  16. F. Birkelbach, M. Winter, U. Flörke, H.-J. Haupt, C. Butzlaff, M. Lengen, E. Bill, A. X. Trautwein, K. Wieghardt and P. Chaudhuri, Inorg. Chem., 1994, 33, 3990 CrossRef CAS.
  17. A. Cornia, A. C. Fabretti, F. Ferraro, D. Gatteschi and A. Giusti, J. Chem. Soc., Dalton Trans., 1993, 3363 RSC.
  18. M. T. Garland, J.-Y. Saillard and E. Spodine, J. Crystallogr. Spectrosc. Res., 1992, 22, 467 CAS.
  19. M. A. Romero, M. N. Moreno, J. Ruiz, M. P. Sanchez and F. Nieto, Inorg. Chem., 1986, 25, 1498 CrossRef CAS; J. Faus, M. Julve, F. Lloret, J. A. Real and J. Sletten, Inorg. Chem., 1994, 33, 5535 CrossRef CAS; K. Tamaki and N. Okabe, Acta Crystallogr., Sect. C, 1996, 52, 1125 CrossRef.
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