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Fabrication and Optimization of Type II Silicon Clathrate Films
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A structural study of Si6-ring-containing [Si6Cl14](2-) chlorosilicates.

Jan Tillmann1, Hans Wolfram Lerner1, Michael Bolte1

  • 1Institut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany.

Acta Crystallographica. Section C, Structural Chemistry
|October 1, 2015
PubMed
Summary

This study presents crystal structures of four substituted-ammonium dichloride dodecachlorosilanes with varying cations and solvents. The dodecachlorosilane ring geometry remains consistent across structures, revealing a chair conformation in the parent molecule.

Keywords:
Si6 ringammonium saltchlorosilicatecrystal structuredodecachlorohexasilane

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Area of Science:

  • Inorganic Chemistry
  • Crystallography
  • Materials Science

Background:

  • Substituted-ammonium salts are crucial in various chemical applications.
  • Dodecahlorosilanes represent a unique class of silicon-based inorganic compounds.
  • Understanding the structural properties of these compounds is key to predicting their behavior.

Purpose of the Study:

  • To elucidate the crystal structures of four novel substituted-ammonium dichloride dodecachlorosilane compounds.
  • To investigate the influence of different cations and solvent molecules on the dodecachlorosilane structure.
  • To determine the conformational preferences of the dodecachlorosilane ring system.

Main Methods:

  • Single-crystal X-ray diffraction was employed to determine the molecular and crystal structures.
  • Analysis of crystallographic data to identify atomic positions, bond lengths, and angles.
  • Comparison of structural parameters across the four distinct crystalline phases.

Main Results:

  • Four crystal structures were successfully determined, each featuring a unique substituted-ammonium cation and varying solvent content.
  • The dodecachlorosilane ring consistently adopts a crystallographic center of inversion in all studied structures.
  • The core geometry of the dichloride dodecachlorosilane unit exhibits remarkable similarity across all investigated compounds, irrespective of the cation or solvent.
  • The parent dodecachlorosilane molecule adopts a chair conformation, providing a baseline for comparison.
  • Disorder in the cation was observed in one structure, with specific atoms and groups occupying multiple sites.

Conclusions:

  • The dodecachlorosilane ring system demonstrates significant structural rigidity and conformational preference.
  • The choice of substituted-ammonium cation and solvent molecules has a minimal impact on the fundamental geometry of the dodecachlorosilane core.
  • The observed chair conformation is a characteristic feature of the parent dodecachlorosilane molecule.
  • Crystallographic studies provide valuable insights into the solid-state behavior of complex inorganic structures.