Phase and structural study of clathrate formation in the [Zn(MePy)2(NCS)2]-MePy system (MePy=4-methylpyridine)

  • J. Lipkowski
  • D. V. Soldatov
  • N. V. Kislykh
  • N. V. Pervukhina
  • Yu. A. Dyadin
Article

Abstract

A phase diagram of the [Zn(MePy)2(NCS)2]-MePy binary system has been studied by DTA and solubility methods. Two compounds melting incongruently (at 63 and 57°C) have been discovered in the system. They have been obtained as separate phases with crystals of different shape (needles and octahedra). Their composition has been determined by analytical methods and verified by X-ray structural analysis: [Zn(MePy)4(NCS)2]·0.67 MePy·xH2O, wherex depends on the synthesis conditions, and [Zn(MePy)4(NCS)2]·MePy, respectively.

The preliminary X-ray study of the first compound (at −100°C) has shown it to be isostructural with the known clathrates of the common formula [M(MePy)4(NCS)2]·0.67MePy·xH2O, where M=Cu, Mn, Mg andx=0–0.33. The unit cell parameters are as follows:a=27.20(1),c=11.202(4) Å, space group\(R\bar 3\),Z=9.

The X-ray study of [Zn(MePy)4(NCS)2]·MePy (at−50°C) has shown it to be analogous to the ‘organic zeolite’ β-phase with the guest MePy molecules located in the channels formed by molecular packing of the [Zn(MePy)4(NCS)2]host. The cell is tetragonal, the space groupI41/a,a=16.845(6),c=23.496(7) Å,V=6667(4) Å3,Z=8,Dcalc=1.289 g cm−3,R=0.074. The zinc cation is surrounded by a slightly irregular octahedron of six nitrogen atoms of the MePy and NCS ligands. The crystallisation field of the host [Zn(MePy)4(NCS)2] complex in the temperature range concerned is absent in the phase diagram. It suggests contact stabilization of the [Zn(MePy)4(NCS)2] molecule by the guest in the clathrates.

Key words

Phase diagram clathrate X-ray structure 4-methylpyridine Zn(II) isothiocyanate 

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Copyright information

© Kluwer Academic Publishers 1994

Authors and Affiliations

  • J. Lipkowski
    • 1
  • D. V. Soldatov
    • 2
  • N. V. Kislykh
    • 2
  • N. V. Pervukhina
    • 2
  • Yu. A. Dyadin
    • 2
  1. 1.Institute of Physical ChemistryPolish Academy of SciencesWarsawPoland
  2. 2.Institute of Inorganic ChemistryRussian Academy of Sciences, Siberian BranchNovosibirskRussia

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