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Structural Pitstops and Turnoffs on the Way to the Birefringent 2-D Layer Structure \(\{\hbox{(tmeda)M[Hg(CN)}_{2}]_{2}\}[\hbox{HgCl}_{4}]\) (M=Cu, Ni)

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Abstract

The reaction of N,N,N′,N′-tetramethylethylenediamine (tmeda) and NiCl2 with the soft, Lewis acidic Hg(CN)2 and HgCl2 in ethanol formed the 2-D layer structure {(tmeda)Ni[Hg(CN)2]2}[HgCl4] (1), isostructural to the Cu(II) analogue. Complex 1 crystallizes in the tetragonal, non-centric \(P \overline{4} {\text{ }}2_{1}\) m space group and contains a 2-D cationic layer of {(tmeda)Ni[Hg(CN)2]2}2+ units in which the six-coordinate Ni(II) centres are bridged by four Hg(CN)2 groups and capped by a tmeda ligand. This array is interspersed with a layer of [HgCl4]2− anions, which form bridging Hg–Cl bonds with the Hg(CN)2 units. The formation of 1 is very sensitive to reaction conditions; the addition of water to the mixture yields the related “structural pitstop” 2-D array {(tmeda)Ni(H2O)[Hg(CN)2]}{[Hg(CN)Cl]2Cl2}·H2O (2), in which the halide migration among Hg(II) centres is incomplete. The larger zero-field splitting D-values of 6.91(1) cm−1 for 1 vs. 2.85(4) cm−1 for 2 indicate that some weak antiferromagnetic interactions are likely present in 1. The reaction of tmeda/Cu(ClO4)2·6H2O with Hg(CN)2 yields [Cu(tmeda)(μ-OH)(ClO4)]2[Hg(CN)2(H2O)2][Hg(CN)2] (3) which is composed of [Cu(tmeda)(μ-OH)(ClO4)]2 dimers in which the \(\hbox{ClO}_4^{-}\) anions cis-bridge the copper(II) centres in the axial positions as well as bind to two adjacent Hg(CN)2 moieties; the perchlorate anion is acting as a rare η4–μ4–ClO4 ligand. N-cyano interactions also exist between the Hg(II) centres; overall, a 2-D corrugated sheet structure which stacks via Cl–O–Hg bridges to yield a 3-D array is formed. The χM T value for 3 decreases with decreasing temperature; a maximum in χM vs. T at 20 K is also observed. This is consistent with antiferromagnetic interactions within the copper(II) dimer, which were fit with the Bleaney-Bowers model to yield J=−23.1(1) cm−1, g=2.113(5) and a paramagnetic impurity P=0.017(1).

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References

  1. K. R. Dunbar and R. A. Heintz, Prog. Inorg. Chem. 45, 283 (1997) and references therein; J. Lefebvre and D. B. Leznoff, in Macromolecules Containing Metal and Metal-like Elements, A. Abd-El-Aziz, C. E. Carraher, C. U. Pittman, J. E. Sheats, and M. Zeldin, eds. (John Wiley and Sons, New York, 2005) Vol. 5

  2. M. Verdaguer, A. Bleuzen, V. Marvaud, J. Vaissermann, M. Seuleiman, C. Desplanches, A. Scuiller, C. Train, R. Garde, G. Gelly, C. Lomenech, I. Rosenman, P. Veillet, C. Cartier and F. Villain, Coord. Chem. Rev. 190–192, 1023 (1999)

    Article  Google Scholar 

  3. M. Ohba and H. Ôkawa, Coord. Chem. Rev. 198, 313 (2000)

    Article  CAS  Google Scholar 

  4. J. S. Miller Inorg. Chem. 39, 4392 (2000)

    Article  CAS  Google Scholar 

  5. T. Iwamoto, in Comprehensive Supramolecular Chemistry, J. M. Lehn, J. L. Atwood, J. E. D. Davies, D. D. MacNicol, F. Vögtle, G. Alberti, and T. Bein, eds. (Pergamon Press, Oxford, 1996)

  6. D. B. Leznoff, B.-Y. Xue, B. O. Patrick, V. Sanchez, and R. C. Thompson, Chem. Commun. 259 (2001)

  7. D. B. Leznoff, B.-Y. Xue, C. L. Stevens, A. Storr, R. C. Thompson, and B. O. Patrick, Polyhedron 20, 1247 (2001)

    Article  CAS  Google Scholar 

  8. D. B. Leznoff, B.-Y. Xue, R. J. Batchelor, F. W. B. Einstein, and B. O. Patrick, Inorg. Chem. 40, 6026 (2001)

    Article  PubMed  CAS  Google Scholar 

  9. J. Lefebvre, R. J. Batchelor, and D. B. Leznoff, J. Am. Chem. Soc. 126, 16117 (2004)

    Article  PubMed  CAS  Google Scholar 

  10. J. Lefebvre and D. B. Leznoff, Gold Bull. 38, 47 (2005)

    Google Scholar 

  11. C. J. Shorrock, B.-Y. Xue, P. B. Kim, R. J. Batchelor, B. O. Patrick, and D. B. Leznoff, Inorg. Chem. 41, 6743 (2002)

    Article  PubMed  CAS  Google Scholar 

  12. N. D. Draper, R. J. Batchelor, B. C. Sih, Z.-G. Ye, and D. B. Leznoff, Chem. Mater. 15, 1612 (2003)

    Article  CAS  Google Scholar 

  13. N. D. Draper, R. J. Batchelor, and L. B. Leznoff, Cryst. Growth Des. 4, 621 (2004)

    Article  CAS  Google Scholar 

  14. N. D. Draper, R. J. Batchelor, P. M. Aguiar, S. Kroeker, and D. B. Leznoff, Inorg. Chem. 43, 6557 (2004)

    Article  PubMed  CAS  Google Scholar 

  15. C. Janiak, Dalton Trans. 2781 (2003)

  16. D. J. Chesnut, D. Hagrman, P. J. Zapf, R. P. Hammond, R. LaDuca, R. C. Haushalter, and J. Zubieta, Coord. Chem. Rev. 192, 737 (1999)

    Article  Google Scholar 

  17. I. J. Hodgkinson and Q. H. Wu, Birefringent Thin Films and Polarizing Elements, World Scientific Publ., River Edge (1997); J. P. Lesso, A. J. Duncan, W. Sibbett, and M. J. Padgett, Appl. Opt. 39, 592 (2000)

  18. V. H. Crawford, H. W. Richardson, J. R. Wasson, D. J. Hodgson, and W. E. Hatfield, Inorg. Chem. 15, 2107 (1976)

    Article  CAS  Google Scholar 

  19. O. Kahn, Molecular Magnetism (VCH, Weinheim, 1993)

    Google Scholar 

  20. E. J. Gabe, P. S. White, and G. D. Enright DIFRAC: A Fortran 77 Control Routine for 4-Circle Diffractometers (N. R. C., Ottawa, 1995)

    Google Scholar 

  21. E. J. Gabe, Y. LePage, J. -P. Charland, F. L. Lee, and P. S. White, J. Appl. Crystallogr. 22, 384 (1989)

    Article  CAS  Google Scholar 

  22. P. W. Betteridge, J. R. Carruthers, R. I. Cooper, C. K. Prout, and D. J. Watkins, J. Appl. Cryst. 36, 487 (2003)

    Article  CAS  Google Scholar 

  23. (a) International Tables for X-ray Crystallography, Vol. IV, Kynoch Press, Birmingham (present distributor Kluwer Academic Publishers: Boston, MA) (1974) p. 99

  24. R. A. Penneman and L. H. Jones J. Inorg. Nucl. Chem. 20, 19 (1961)

    Article  CAS  Google Scholar 

  25. D. Grdenic, Quart. Rev. 19, 303 (1965)

    Article  CAS  Google Scholar 

  26. W. E. Hatfield, in Magneto-Structural Correlations in Exchange Coupled Systems W.R. Dillett, D. Gatteschi, and O. Kahn, eds. (Reidel, Dordrecht, 1984), pp. 555

    Google Scholar 

  27. F. Haftbaradaran, D. B. Leznoff, and V. E. Williams, Dalton Trans. 2105 (2003)

  28. H. Oshio, T. Watanabe, A. Ohto, T. Ito, and U. Nagashima, Angew. Chem., Int. Ed. Engl. 33, 670 (1994)

    Article  Google Scholar 

  29. H. Oshio, T. Watanabe, A. Ohto, T. Ito, T. Ikoma, and S. Tero-Kubota, Inorg. Chem. 36, 3014 (1997)

    Article  PubMed  CAS  Google Scholar 

  30. B. Bleaney and K. D. Bowers, Proc. R. Soc. London A 214, 451 (1952)

    Article  CAS  Google Scholar 

  31. E. Ruiz, P. Alemany, S. Alvarez, and J. Cano, J. Am. Chem. Soc. 119, 1297 (1997)

    Article  CAS  Google Scholar 

  32. E. Ruiz, P. Alemany, S. Alvarez, and J. Cano, Inorg. Chem. 36, 3683 (1997)

    Article  PubMed  CAS  Google Scholar 

  33. H. Hu, Y. Liu, D. Zhang, and C. Liu, J. Mol. Struct. 546, 73 (2001)

    CAS  Google Scholar 

  34. K. T. McGregor, N. T. Watkins, D. L. Lewis, R. F. Drake, D. J. Hodgson, and W. E. Hatfield, Inorg. Nucl. Chem. Lett. 9, 423 (1973)

    Article  CAS  Google Scholar 

  35. G. A. van Albada, I. Mutikainen, U. Turpeinen, and J. Reedijk, Inorg. Chim. Acta 324, 273 (2001) and references therein

  36. I. Castro, J. Faus, M. Julve, C. Bois, J. A. Real, and F. Lloret, J. Chem. Soc., Dalton Trans. 47 (1992)

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Acknowledgments

Financial support from NSERC (D.B.L.) and Natural Resources Canada (N.D.D., M.J.K.) are gratefully acknowledged.

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Authors and Affiliations

  1. Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, BC, V5A 1S6, Canada

    Neil D. Draper, Michael J. Katz, Raymond J. Batchelor & Daniel B. Leznoff

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  1. Neil D. Draper
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  2. Michael J. Katz
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  3. Raymond J. Batchelor
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  4. Daniel B. Leznoff
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Correspondence to Daniel B. Leznoff.

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Special Issue to honour Professor Richard J. Puddephatt

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Draper, N., Katz, M., Batchelor, R. et al. Structural Pitstops and Turnoffs on the Way to the Birefringent 2-D Layer Structure \(\{\hbox{(tmeda)M[Hg(CN)}_{2}]_{2}\}[\hbox{HgCl}_{4}]\) (M=Cu, Ni). J Inorg Organomet Polym 15, 447–458 (2005). https://doi.org/10.1007/s10904-006-9017-z

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