On the Two Closely Related Phases of [Ru(C5Me5)(η6-1,3-(Me2NCH2)2C6H4)](BF4) and the Reversible Solid–Solid Order–Disorder Phase Transition
- 70 Downloads
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.
KeywordsSolid–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).
- 6.Sielger MA (2007) PhD Dissertation, University of Kentucky. http://lib.uky.edu/ETD/ukychem2007d00664/dissertationMASiegler.pdf
- 7.Bernstein J (2002) Polymorphism in molecular crystals. Oxford University Press, USAGoogle Scholar
- 12.Nonius (1999) COLLECT; Nonius BV, Delft, The NetherlandsGoogle Scholar
- 13.Schreurs AMM (2005) PEAKREF. University of Utrecht, The NetherlandsGoogle Scholar
- 16.Beurskens PT, Beurskens G, de Gelder R, Garcia-Granda S, Gould RO, Israel R, Smits JMM (1999) The DIRDIF99 program system. Technical Report of the Crystallography Laboratory, University of Nijmegen, The NetherlandsGoogle Scholar
- 17.Sheldrick GM (1986) SHELXS86. University of Göttingen, GermanyGoogle Scholar
- 19.Sheldrick GM (1999-2003) SADABS. University of Göttingen, GermanyGoogle Scholar
- 20.Sheldrick GM (2003) TWINABS. University of Göttingen, GermanyGoogle Scholar