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The Geometrical Isomerization on Acidification in Hexamolybdoheteropoly Oxometalate. The Crystal Structure of $(NH_{4})_{4.5}[H_{3.5}\alpha-PtMo_{6}O_{24}].\;1.5H_{2}O,\;(NH_{4})_{4}[H_{4}\beta-PtMo_{6}O_{24}].\;1.5H_{2}O,\;and\;K_{3.5}[H_{4.5}\alpha-PtMo_{6}O_{24}].\;3H_{2}O$

  • Lee, Uk (Department of Chemistry, National Fisheries University of Pusan) ;
  • Yukiyoshi Sasaki (Department of Chemistry. The University of Tokyo)
  • 발행 : 1994.01.20

초록

$(NH_4)_{4.5}[H_{3.5}{\alpha}-PtMo_6O_{24}]{\cdot}1.5\;H_2O(A),\;(NH_4)_4[H_4{\beta}-PtMo_6O_{24}]{\cdot}1.5\;H_2O(B),\;and\;K_{3.5}[H_{4.5}{\alpha}-PtMo_6O_{24}]{\cdot}3\;H_2O(C)$ have been synthesized and their molecular structures have been also determined by single-crystal X-ray diffraction technique. The space groups, unit cell parameters, and R factors are as follows: Compound A, monoclinic, $A_{2/a}$, a= 19.074 (3), b=21.490 (3), c=15.183 (2) ${\AA};\;{\beta}$=109.67 (1) ${\AA}$; z=8; R=0.075($IF_0I>4{\sigma}(IF_0I);$ Compound B, triclinic, P$bar{1}$, a=10.776 (2), b=15.174 (4), c=10.697 (3) ${\AA};\;{\alpha}$ =126.29 (2), ${\beta}$=111.55 (2), ${\gamma}$=93.18 (2) ${\AA}$; Z=2; R=0.046($IF_0I>3{\sigma}(IF_0I);$): Compound C, triclinic, Pl, a=12.426 (2), b=13.884 (2), c=10.089 (1) ${\AA}$; ${\alpha}$=102.59 (2), ${\beta}$=110.73 (1), ${\gamma}$=53.93 (1) ${\AA}$; Z=2; R=0.074 ($IF_0I>3{\sigma}(IF_0I)$. Compounds A and C contain the well-known Anderson structure (planar structure) heteropoly oxometalate having approximate $bar{3}_m(D_{3d})$ symmetry, while compound B contains the bent structure heteropoly oxometalate having appproximate $2_{mm}(C2_v)$ symmetry. The bent structure and the planar one are geometrical isomers. These compounds are rot only novel heteroply molybdates containing platinate(IV) but also the first example of geometrical isomerism in the hexamolybdoheteropoly oxometalates. That isomerization surprisingly occurred because of the change of only 0.5 non-acidic hydrogen atom attached to the polyanion such as $[H_{3.5}{\alpha} -PtMo_6O_{24}]^{4.5-}{\to}[H_4{\beta}-PtMo_6O_{24}]^{4-}{\to}[H_{4.5}{\alpha} -PtMo_6O_{24}]^{3.5-}$. It seems that the gradual protonation of the polyanion plays an important role in that isomerism. These heteropolyanions form dimers by strong hydrogen bonds between two heteropolyanions in the respective crystal system.

키워드

참고문헌

  1. Inorg. Chem. v.16 Massart, R.;Contant, R.;Fruchart, J. M.;Ciabrini, J. P.;Fournier, M.
  2. Naturforsch. Teil B. v.36 Fuchs, J. P.;Thile, A.;Palm, R. Z.
  3. J. Chem. Res.(S). Contant, R.;Ciabrini, J. P.
  4. Chem. Uses Molybdenum. Proc. Int. Conf. 3rd. Kazansky, L. P.;Potapova, I. V.;Spitsyn, V. I.
  5. Naturforsch. Teil B. v.36 Fuchs, J. ;Thile, A.;Palm, R. Z.
  6. Acta Crystallogr. v.B36 Ichida, H.;Kobayashi, A.;Sasaki, Y.
  7. Acta Crystallogr. v.B33 Brown, G. M.;Noe-Spirlet, M. R.;Busing, W. R.;Levy, H. A.
  8. Kristallogr. Kristallogeom. Kristallphys. Kristallchem. v.143 Damour, H.;Allmann, R. A.
  9. Acta Crystallogr. v.B33 Strandberg, R.
  10. Acta Crystallogr. v.B30 Evans, H. T. Jr.
  11. Acta Crystallogr. v.B36 Kondo, H.;Kobayashi, A.;Sasaki, Y.
  12. Inorg. Chem. v.9 Perloff, A.
  13. Bull. Korean Chem. Soc. v.11 Nagano, O.;Lee, U.;Ichida, H.;Sasaki, Y.
  14. Acta Crystallogr. v.C47 Lee, H. Y.;Park, K. M.;Lee, U.;Ichida, H.
  15. Acta Crystallogr. v.C45 Ito, F.;Ozeki, T.;Ichida, H.;Sasaki, Y.
  16. Acta Crystallogr. v.C47 Ozawa, Y.;Hayashi, Y.;Isobe, K.
  17. Acta Crystallogr. v.C42 Schuidt, K. J.;Schrobilgen, G. J.
  18. Bull. Korean Chem. Soc. v.8 Lee, U.;Sasaki, Y.
  19. Koore. Khim. v.5 Sergienko, V. S.;Molchanov, V. N.;Porai-Koshits, M. V.;Torchenkova, E. A.
  20. Acta Crystallogr. v.C40 Lee, U.;Ichida, H.;Kobayashi, A.;Sasaki, Y.
  21. Acta Crystallogr. v.C39 Lee, U.;Kobayashi, A.;Sasaki, Y.
  22. J. Korean Chem. Soc. v.31 Lee, U.;Sasaki, Y.
  23. Acta Crystallogr. v.C44 Ogawa, A.;Yamato, H.;Lee, U.;Ichida, H.;Sasaki, Y.
  24. Arkiv. Kemi. v.2 Lindqvist, I.
  25. Acta Chem. Scand. v.27 Sjobom, K.;Hedman, B.
  26. J. Chem. Soc., Dalton Trans. Evans Jr., H. T.;Gatehouse, B. M.;Leverett, P.
  27. Chem. Lett. Lee, U.;Sasaki, Y.
  28. Bull. Korean Chem. Soc. v.9 Lee, U.
  29. Am. Chem. J. v.17 Gibbs, W.
  30. International Tables for X-ray Crystallography v.IV Kynoch Press
  31. Rep. Inst. Phys. And Chem. Res. v.55 Sakurai, T.;Kobayashi, K.
  32. Anorg. Allg. Chem. v.414 Tromel. von M.;Lupprich, E. Z.
  33. Acta Crystallogr. v.7 Simons, W. J.;Templeton, D. H.

피인용 문헌

  1. Crystal Structure of Cesium Salt of β-Isomer of A-Type Vanadium-Trisubstituted Dodecatungstophosphate Anion, A-β-Cs5.4H0.6[PV3W9O40] vol.70, pp.10, 1994, https://doi.org/10.1246/bcsj.70.2455
  2. Edelmetalle in Polyoxometallaten vol.124, pp.38, 1994, https://doi.org/10.1002/ange.201202750
  3. Noble Metals in Polyoxometalates vol.51, pp.38, 1994, https://doi.org/10.1002/anie.201202750