This paper describes the structures of pseudo-18-crown-6 compounds (2, R,R-4 and 5) in the crystals together with theoretical calculations of the electronic circular dichroism (ECD) spectra. The achiral macrocyclic phosphinic acid 5 forms hydrogen-bonded dimers in the crystal. The O1–O2 distance (2.489 Ǻ) indicates strong H-bondings. The conformations of the macrorings of the achiral phosphinate 2 and the monomers of the achiral phosphinic acid 5 are chiral. A comparison of the torsion angles of the achiral methyl phosphinate 2 and the monomeric units of achiral 5 indicates a similar geometry. The torsion angles of the chiral methyl phosphinate (R,R)-4 differ more significantly from those in achiral methyl phosphinate 2. A negative 1Bb exciton couplet was observed in the ECD spectrum of monomeric (R,R)-6 in MeOH and H2O as in the spectra of (R,R)-4 in all solvents. To support the idea that (R,R)-4 has basically the same conformation in the crystal and in solution, the ECD spectrum of (R,R)-4 was calculated using the geometry of the molecule in the crystal. The calculated ECD spectrum shows a reasonable agreement with the ECD spectra obtained in solution. This shows that the steric structure observed in the crystal is predominant in solution as well.
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This work was supported by the Hungarian Scientific Research Fund (OTKA K62654 to P.H., PD71817 to V.F., PD71910 to T.T. and NI68466 to M.H.) and GVOP-3.2.1-2004-04-0345/3.0. The HPC Group computer facility, University of Szeged was used for several computations.
Dedicated to Professor Károly Lempert on the occasion of his 85th birthday.
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Székely, G., Farkas, V., Párkányi, L. et al. Crystal structures of crown ethers containing an alkyl diarylphosphinate or a diarylphosphinic acid unit. Struct Chem 21, 277–282 (2010). https://doi.org/10.1007/s11224-010-9581-2
- Crown ethers
- Diarylphosphinic acids
- X-ray analysis
- Computed ECD spectra