Crystal structure and DFT calculations of andrographiside

doi:10.1016/j.molstruc.2009.11.036

Journal of Molecular Structure

Volume 965, Issues 1–3, 25 February 2010, Pages 45-49

Dedication: This work is dedicated to Late Kinkini Bhattacharya of the Department of Materials Science, IACS.

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Abstract

Crystal and molecular structure of a labdane diterpenoid glucoside, andrographiside (1) is determined from 2D-NMR and X-ray diffraction data. The 2D-NMR study indicates that the carbohydrate moiety is in β-linkage and the sugar moiety is linked to C-19 of the aglycon. These observations are further confirmed from the X-ray diffraction studies. Both the six-membered rings are in chair conformation whereas the glucose ring adopts a twist-boat conformation. The molecular geometries and electronic structure of (1) were calculated at the DFT level using the hybrid exchange–correlation functional, BLYP, PW91 and PBE.

Introduction

The title compound andrographiside is a labdane diterpenoid glucoside isolated from the leaves of Andrographis paniculata Nees (Acanthaceac oilments). The plant is a small annual herb widely distributed throughout the greater part of India and Southeast Asia. It enjoys considerable reputation for its wide spectrum of biological activities including antibacterial, anti inflammatory, antimalarial, hepatoprotective etc. and used in Ayurvedic system of medicine for various ailments [1]. Earlier investigations showed that the plant is a rich source of labdane diterpenoids and their glycosides [2]. The biological activities of A. paniculata have been attributed to its constituents. It has found that andrographiside was more potent hepatoprotective agent than andrographolide [3]. The structure of andrographiside has been earlier confirmed from 1D ¹H and ¹³C NMR spectra [4]. As part of our ongoing studies to elucidate the relationships between the characteristics of the functional dyes containing andrographolide skeleton and their molecular structures and to investigate the possibilities for intra- and intermolecular hydrogen bonding in the solid state, the X-ray structure analysis was undertaken. In continuation of our work [5], we have now carried out the X-ray structural analysis to confirm the result obtained from spectroscopic studies of (1) along with the DFT calculations to investigate the molecular geometry and electronic structure.

Section snippets

Preparation of andrographiside

The air dried powdered leaves of A. paniculata were successively extracted with petroleum ether (333–353 K), chloroform and methanol at ambient temperature. The concentrated methanol extract was partitioned between n-BuOH and water. The n-BuOH fraction was dried to give a greenish brown mass which was chromatographed over a column of silica gel. Andrographiside was eluted with chloroform–methanol mixture (9:1). Tiny crystals of andrographiside were obtained from a solution of the compound in

Structural description

The structure of the molecule was initially deduced from detailed NMR spectral analysis. 2D-NMR spectral results permitted unambiguous assignment of chemical shifts to all protons and carbons. The β-linkage of the glucose moiety was evident from the large coupling constant (7.8 Hz) of the anomeric proton signal (d 4.87,d). Sugar–aglycone linkage was deduced unequivocally from the HMBC and NOESY spectral results. Thus correlation peaks in the HMBC spectrum between the signals of C-19 (d 72.3) of

Conclusion

The 2D-NMR study indicates that the carbohydrate moiety is in β-linkage and the sugar moiety is linked to C-19 of the aglycon. The X-ray structural analysis has confirmed the result obtained from spectroscopic studies. The molecular geometry and the electronic structure of the title compound have been analyzed by the DFT calculations. The observed molecular conformations of the title compound from X-ray analysis agree well with that obtained from the quantum mechanical calculations. The

Supplementary data

Crystallographic data (excluding structure factors) for the structures reported in this article have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication number CCDC 659566 of compound (1). Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK. Fax: +44 1223 336033; e-mail: [email protected] .

Acknowledgements

S.K. Seth is grateful to the DST-funded National Single Crystal X-ray Diffraction facility at the Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata, India for data collection. The authors thank Dipak K. Hazra, Department of Solid State Physics, IACS, for his interest, helping in DFT calculations and stimulating discussions.

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Crystal structure and DFT calculations of andrographiside

Abstract

Introduction

Section snippets

Preparation of andrographiside

Structural description

Conclusion

Supplementary data

Acknowledgements

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Theor. Chem. Acc.

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The Wealth of India, A Dictionary of Indian Raw Materials & Industrial Products (volume 1: A, Revised edition)

J. Nat. Prod.

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Acta Cryst. E

SHELXL97, Programs for Crystal Structure Analysis

WinGX-A windows program for crystal structure analysis

J. Appl. Crystallogr.