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Hydro/solvothermal synthesis, crystal structure, and thermal behaviour of piperazine-templated nickel(II) and cobalt(II) sulfates

  • Kim, Chong-Hyeak (Center for Chemical Analysis, Korea Research Institute of Chemical Technology) ;
  • Park, Chan-Jo (Center for Chemical Analysis, Korea Research Institute of Chemical Technology) ;
  • Lee, Sueg-Geun (Center for Chemical Analysis, Korea Research Institute of Chemical Technology)
  • Received : 2006.06.27
  • Accepted : 2006.08.04
  • Published : 2006.08.28

Abstract

Two piperazine-templated metal sulfate complexes, $(C_4N_2H_{12})[Ni(H_2O)_6](SO_4)_2$, I and ($C_4N_2H_{12}$) $[Co(H_2O)_6](SO_4)_2$, II, have been synthesized by hydro/solvothermal reactions and their crystal structures analyzed by single crystal X-ray diffraction methods. Complex I crystallizes in the monoclinic system, $P2_1/n$ space group, a=12.920(3), b=10.616(2), $c=13.303(2){\AA}$, ${\beta}=114.09(1)^{\circ}$, Z=4, $R_1=0.030$ for 3683 reflections; II: monoclinic $P2_1/n$, a=12.906(3), b=10.711(2), $c=13.303(2){\AA}$, ${\beta}=114.10(2)^{\circ}$, Z=4, $R_1=0.032$ for 4010 reflections. The crystal structures of the piperazine-templated metal(II) sulfates demonstrate zero-dimensional compound constituted by diprotonated piperazine cations, metal(II) cations and sulfate anions. The structures of complex I and II are substantially isostructural to that of the previously reported our piperazine-templated copper(II) sulfate complex $(C_4N_2H_{12})[Cu(H_2O)_6](SO_4)_2$. The central metal(II) atoms are coordinated by six water molecules in the octahedral geometry. The crystal structures are stabilized by three-dimensional networks of the $O_{water}-H{\cdots}O_{sulfate}$ and $N_{pip}-H{\cdots}O_{sulfate}$ hydrogen bonds between the water molecules and sulfate anions and protonated piperazine cations. Based on the results of thermal analysis, the thermal decomposition reactions of the complex I was analyzed to have three distinctive stages whereas the complex II proceed through several stages.

Keywords

References

  1. A. K. Cheetham, G. Ferey, T. Loiseau, Angew. Chem., Int. Ed., 38, 3268 (1999) https://doi.org/10.1002/(SICI)1521-3773(19991115)38:22<3268::AID-ANIE3268>3.0.CO;2-U
  2. A. Clearfield, Chem. Rev., 88, 125 (1988) https://doi.org/10.1021/cr00083a007
  3. G. Alberti, Comprehensive Supramolecular Chemistry, Vol. 7, Chap. 4 & 5, J. L. Atwood, J. E. D. Davies, D. D. MacNicol, and F. Vogtle, Eds., Pergamon Press, New York, U.S.A., 1996
  4. C. N. R. Rao, S. Natarajan, R. Vaidhyanathan, Angew. Chem., Int. Ed., 43, 1466 (2004) https://doi.org/10.1002/anie.200300588
  5. S. M. Walker, P. S. Halasyamani, D. O'Hare, J. Am. Chem. Soc., 121, 7415 (1999) https://doi.org/10.1021/ja9912271
  6. T. Conradsson, X. Zou, M. Dadachov, Inorg. Chem., 39, 1716 (2000) https://doi.org/10.1021/ic9911217
  7. S. Ekambarem, S. Sevov, Inorg. Chem., 39, 2405 (2000) https://doi.org/10.1021/ic991367b
  8. A. Choudhury, U. Kuma, C. N. R. Rao, Angew. Chem., Int. Ed., 41, 158 (2002) https://doi.org/10.1002/1521-3773(20020104)41:1<158::AID-ANIE158>3.0.CO;2-#
  9. J. N. Behera, K. V. Gopalkrishnan, C. N. R. Rao, Inorg. Chem., 43, 2636 (2004) https://doi.org/10.1021/ic035488u
  10. Y. Xing, Z. Shi, G. Li, W. Pang, J. Chem. Soc., Dalton Trans., 940 (2003)
  11. A. J. Norquist, P. M. Thomas, M. B. Doran, D. O'Hare, Chem. Mater., 14, 5179 (2002) https://doi.org/10.1021/cm020793j
  12. M. I. Khan, S. Cevik, R. J. Doedens, Inorg. Chim. Acta, 292, 112 (1999) https://doi.org/10.1016/S0020-1693(99)00153-X
  13. M. B. Doran, A. J. Norquist, D. O'Hare, Inorg. Chem., 42, 6989 (2003) https://doi.org/10.1021/ic025647u
  14. C. H. Kim, C. J. Park, S. G. Lee, Anal. Sci. & Tech., 18, 381 (2005)
  15. K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part B, John Wiley & Sons, New York, U.S.A., 1997
  16. Siemens, XSCANS Data Collection Package, Siemens, Karlsruhe, Germany, 1996
  17. Siemens, SHELXTL Structure Analysis Package, Siemens, Karlsruhe, Germany, 1998
  18. G. M. Sheldrick, Acta Cryst., A46, 467 (1990)
  19. G. Paul, A. Choudhury, R. Nagarajan, C. N. R. Rao, Inorg. Chem., 42, 2004 (2003) https://doi.org/10.1021/ic025647u
  20. K. Jayaraman, A. Choudhury, C. N. R. Rao, Solid State Sci., 4, 413 (2002) https://doi.org/10.1016/S1293-2558(02)01269-4