Journal of Chemical Crystallography

, Volume 40, Issue 9, pp 753–760 | Cite as

On the Two Closely Related Phases of [Ru(C5Me5)(η6-1,3-(Me2NCH2)2C6H4)](BF4) and the Reversible Solid–Solid Order–Disorder Phase Transition

  • Maxime A. Siegler
  • Sylvestre Bonnet
  • Antoine M. M. Schreurs
  • Robertus J. M. Klein Gebbink
  • Gerard van Koten
  • Anthony L. Spek
Original Paper


Crystals of the complex [Ru(C5Me5)(η6-1,3-(Me2NCH2)2C6H4)](BF4) have been examined over the temperature range 150–300 K via X-ray diffraction measurements. This study shows that the Ru complex is a two-phase system in this T-range and the solid–solid transition is reversible. At 150 K, phase II (P21/c, Z′ = 4) is ordered and non-merohedrally twinned, a = 16.4396 (9) Å, b = 17.3226 (4) Å, c = 32.1874 (11) Å, β = 91.375 (2)°. At 295 K, phase I (Pbca, Z′ = 1) is disordered, a = 8.5071 (3) Å, b = 17.1567 (3) Å, c = 32.8250 (8) Å. The relationship between the two phases is obvious because the packing remains similar in the two phases. The greatest structural changes between the two phases are found in the rows of adjacent cations [Ru(C5Me5)(η6-1,3-(Me2NCH2)2C6H4)]+ packed along the a direction. These rows are ordered in phase II but are disordered in phase I. The phase transition is first order. Significant changes in thermal motion for the cations are considered as being the driving force for the occurrence of this phase transition.

Graphical Abstract

The X-ray diffraction study showed that the complex [Ru(C5Me5)(η6-1,3-(Me2NCH2)2C6H4)](BF4) is a two-phase system between 150 and 300 K.


Solid–solid phase transition Polymorphism First-order 



We gratefully acknowledge the support of this research by Utrecht University and the NRSC-Catalysis program. This work was also supported in part (A.L.S.) by the Council for the Chemical Sciences of The Netherlands Organization for Scientific Research (CW-NWO).

Supplementary material

10870_2010_9732_MOESM1_ESM.doc (1.2 mb)
DOC 1237 kb)


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Copyright information

© Springer Science+Business Media, LLC 2010

Authors and Affiliations

  • Maxime A. Siegler
    • 1
    • 3
  • Sylvestre Bonnet
    • 2
    • 4
  • Antoine M. M. Schreurs
    • 1
  • Robertus J. M. Klein Gebbink
    • 2
  • Gerard van Koten
    • 2
  • Anthony L. Spek
    • 1
  1. 1.Crystal and Structural Chemistry, Bijvoet Center for Biomolecular Research, Faculty of ScienceUtrecht UniversityUtrechtThe Netherlands
  2. 2.Organic Synthesis and Catalysis, Debye Institute for Nanomaterials Science, Faculty of ScienceUtrecht UniversityUtrechtThe Netherlands
  3. 3.Department of ChemistryThe Johns Hopkins UniversityBaltimoreUSA
  4. 4.Leiden Institute of Chemistry, Gorlaeus LaboratoriesLeiden UniversityLeidenThe Netherlands

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