Synthesis, Crystal Structure and Theoretical Characterization of (3R, 4R, 6S)-3,6-Dihydroxy-1- Menthene Isolated from Echinophora Tenuifolia

Abstract

In the title compound, C₁₀H₁₈O₂, the cyclohexene ring adopts a half-chair conformation. In the crystal strcuture, weak inter­molecular O—H . . . O hydrogen bonds connect the adjacent molecules, forming edge-fused R₂³(8) ring motifs, into the hollow columns parallel to the b-axis direction. The crystal packing is governed only by van der Waals inter­actions. There is further no exist C—H···π and π-π interactions. The H atom in the one of two hydroxyl groups was found to be disordered over two site. The occupancy factors of the two sites were refined to 0.52 (2) and 0.48 (2). Semi-empirical PM3 quantum chemical calculations are in satisfactory agreement with the results of the X-ray structure analysis.

Keywords

• crystal structure
• cyclohexene ring; 2-methyl-5-(propan-2-yl)cyclohex-2-ene-1
• 4-diol; semi-empirical PM3 quantum chemical calculations; HOMO and LUMO energy levels.

References

1. Özcan, M. and Akgül, A. “Essential oil composition of Turkish pickling herb (Echinophora tenuifolia L. Subsp. Sibthorpiana (Guss.) Tutin)”, Acta Botanica Hungarica, 45(1): 163-167, (2003).
2. Telci, I. and Hisil, Y., “Essential Oil Composition of the Spice Plant Echinophora tenuifolia L. Subsp sibthorpiana Tutin from Turkey”, Chemistry of Natural Compounds, 44(4): 534-536, (2008).
3. Chalchat, J. C., Ozcan, M. M., Dagdelen, A. and Akgul, A. “Variability of essential oil composition of Echinophora tenuifolia subsp sibthorpiana tutin by harvest location and year and oil storage”, Chemistry of Natural Compounds, 43(2): 225-227, (2007).
4. Georgiou, C., Koutsaviti, A., Bazos, I. and Tzakou, O. “Chemical composition of Echinophora tenuifolia subsp sibthorpiana essential oil from Greece”, Records of Natural Products, 4(3): 167-170, (2010).
5. Gokbulut, I., Bilenler, T. and Karabulut, I. “Determination of Chemical Composition, Total Phenolic, Antimicrobial, and Antioxidant Activities of Echinophora tenuifolia Essential Oil”, International Journal of Food Properties, 16(7): 1442-1451, (2013).
6. Sheldrick, G. M. “SADABS: Software for Empirical Absorption Correction”, University of Gottingen, Institute fur Anorganische Chemieder Universitat, Gottingen, Germany, (2003).
7. Sheldrick, G. M. “A short history of SHELX“, Acta Crystallographica, A64(1): 112–122, (2008).
8. Sheldrick, G. M. “Crystal structure refinement with SHELXL”, Acta Crystallograhica, C71(1): 3–8, (2015).

9. Cremer, D. and Pople, J. A. “A general definition of ring puckering coordinates”, J. Am. Chem. Soc., 97, 1354–1358, (1975).
10. Boualy, B., Harrad, M. A., Firdoussi, L. E., Ali, M. A. and Rizzoli, C. “(S)-4-(2-Chloro-propan-2-yl)-1-(2,2,2-tri¬chloro¬eth¬yl)cyclo¬hexene”, Acta Crysallographica, E67(4): o960, (2011).
11. Smrcok, L., Mach, P. and Le Bail, A. “Deca¬fluoro¬cyclohex-1-ene at 4.2 K – crystal structure and theoretical analysis of weak interactions”, Acta Crystallographica, B69(8): 395–404, (2013).
12. Maharramov, A. M., Allahverdiyev, M. A., Mammadov, E. Y., Askerova, A. R. and Rashidov, B. A. “rac-2-tert-Butyl-2,4,5,6,6-penta¬chloro¬cyclo¬hex-3-en-1-one”, Acta Crystallographica, E67(4), o881, (2011).
13. Bernstein, J., Davis, R. E., Shimoni, L. and Chang, N.-L. “Patterns in Hydrogen Bonding: Functionality and Graph Set Analysis in Crystals”, Angew. Chem. Int. Ed. Engl., 34: 1555–1573, (1995).
14. Stewart, J. J. P. “MOPAC. QCPE Program 445. Quantum Chemistry Program Exchange”, Indiana University, Bloomington, IN 47405, USA, (1985).