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Volume 64 
Part 3 
Pages o585-o586  
March 2008  

Received 21 November 2007
Accepted 24 November 2007
Online 13 February 2008

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© International Union of Crystallography 2008

Key indicators
Single-crystal X-ray study
T = 103 K
Mean [sigma](C-C) = 0.002 Å
R = 0.041
wR = 0.101
Data-to-parameter ratio = 24.3
Details
Open access

A second polymorph of [beta]-arteether

Jerry P. Jasinski,a* Ray J. Butcher,b H. S. Yathirajan,c B. Narayanad and T. V. Sreevidyad

aDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA,bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA,cDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and dDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India
Correspondence e-mail: jjasinski@keene.edu

The crystal structure of the title compound, C17H28O5, reported here is a polymorph of the structure first reported by El-Feraly, Al-Yahya, Orabi, McPhail & McPhail [J. Nat. Prod. (1992). 55, 878-883]. It is a derivative of the antimalaria compound artemisinin and consists primarily of three substituted ring systems fused together. A cyclohexane ring (distorted chair conformation) fused to a tetrahydropyran group (distorted chair) is adjacent to an oxacycloheptane unit containing an endo-peroxide bridge, giving the molecule its particular three-dimensional arrangement. The crystal packing is stabilized by intermolecular C-H...O interactions between an O atom from the endo-peroxide bridge and H atoms from both the cyclohexane and seven-membered oxacycloheptane fused rings, as well as between an O atom and H atom from adjacent tetrahydropyran rings. The two polymorphs have the same space group and similar cell parameters for the a and b axes, but significantly different values for the c axis.

Related literature

For the first polymorph of this compound, see: El-Feraly et al. (1992[El-Feraly, F. S., Al-Yahya, M. A., Orabi, K. Y., McPhail, D. R. & McPhail, A. T. (1992). J. Nat. Prod. 55, 878-883.]). For crystal structures of similar compounds, see: Brossi et al. (1988[Brossi, A., Venugopalan, B., Dominguez Gerpe, L., Yeh, H. J. C., Flippen-Anderson, J. L., Buchs, P., Luo, X. D., Milhousand, W. & Peters, W. (1988). J. Med. Chem. 31, 645-650.]); Flippen-Anderson et al. (1989[Flippen-Anderson, J. L., George, C., Gilardi, R., Yu, Q.-S., Dominguez, L. & Brossi, A. (1989). Acta Cryst. C45, 292-294.]); Karle & Lin (1995[Karle, J. M. & Lin, Ai. J. (1995). Acta Cryst. B51, 1063-1068.]); Li et al. (2006[Li, S.-H., Yue, Z.-Y., Gao, P. & Yan, P.-F. (2006). Acta Cryst. E62, o1898-o1900.]); Luo et al. (1984[Luo, X. D., Yeh, H. J. C., Brossi, A., Flippen-Anderson, J. L. & Gillardi, R. (1984). Helv. Chim. Acta, 67, 1515-1522.]); Yue et al. (2006[Yue, Z.-Y., Li, S.-H., Gao, P., Zhang, J.-H. & Yan, P.-F. (2006). Acta Cryst. C62, o281-o282.]); Butcher et al. (2007[Butcher, R. J., Jasinski, J. P., Yathirajan, H. S., Bindya, S. & Narayana, B. (2007). Acta Cryst. E63, o3291-o3292.]); Jasinski et al. (2008[Jasinski, J. P., Butcher, R. J., Yathirajan, H. S., Narayana, B. & Sreevidya, T. V. (2008). Acta Cryst. E64, o89-o90.]). For biological activity of artemisinin derivatives in vitro and in vivo, see: Grace et al. (1998[Grace, J. M., Aguilar, A. J., Trotman, K. M. & Brewer, T. G. (1998). Drug Metab. Dispos. 26, 313-317.]); Li et al. (2001[Li, Y., Shan, F., Wu, J. M., Wu, G. S., Ding, J., Xiao, D., Yang, W. Y., Atassi, G., Leonce, S., Caignard, D. H. & Renard, P. (2001). Bioorg. Med. Chem. Lett. 11, 5-8.]); Maggs et al. (2000[Maggs, J. L., Bishop, L. P. D., Edwards, G., O'Neill, P. M., Ward, S. A., Winstanley, P. A. & Park, K. (2000). Drug Metab. Dispos. 28, 209-217.]); Yang et al. (1997[Yang, X. P., Pan, Q. C., Liang, Y.-G. & Zikang, Y.-L. (1997). Cancer, 16, 186-187.]). For endo-peroxide sesquiterpene lactone derivatives, see: Saxena et al. (2003[Saxena, S., Pant, N., Jain, D. C. & Bhakuni, R. S. (2003). Curr. Sci. 85, 1314-1329.]); Venugopalan et al. (1995[Venugopalan, B., Karnik, P. J., Bapat, C. J., Chatterjee, D. K., Iyer, N. & Lepcha, D. (1995). Eur. J. Med. Chem. 30, 697-706.]); Wu et al. (2001[Wu, J. M., Shan, F., Wu, G. S., Ying, L., Ding, J., Xiao, D., Han, J.-X., Atassi, G., Leonce, S., Caignard, D. H. & Renard, P. (2001). Eur. J. Med. Chem. 36, 469-479.]). For the synthesis of artemisinin and its derivatives, see: Lui et al. (1979[Lui, J.-M., Ni, M.-Y., Fan, Y.-E., Tu, Y.-Y., Wu, Z.-H., Wu, Y.-L. & Chou, W.-S. (1979). Acta Chim. Sinica, 37, 129-141.]); Liu (1980[Liu, X. (1980). Chin. Pharm. Bull. 15, 183-183.]); Robert et al. (2001[Robert, A., Benoit-Vical, F., Dechy-Cabaret, O. & Meunier, B. (2001). Pure Appl. Chem. 73, 1173-1188.]). For related literature, see: Cremer & Pople (1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]); Lisgarten et al. (1998[Lisgarten, J., Potter, B. S., Bantuzeko, C. & Palmer, A. (1998). J. Chem. Crystallogr. 28, 539-542.]); Qinghaosu Research Group (1980[Qinghaosu Research Group (1980). Sci. Sin. (Engl. Ed.), 23, 380-396.]); Shen & Zhuang (1984[Shen, C. C. & Zhuang, L. (1984). Med. Res. Rev. 4, 57-59.]); Wu & Li (1995[Wu, Y.-L. & Li, Y. (1995). Med. Chem. Res. 5, 569-586.]).

[Scheme 1]

Experimental

Crystal data

  • C17H28O5

  • Mr = 312.39

  • Trigonal, P 32 21

  • a = 10.0253 (6) Å

  • c = 28.628 (3) Å

  • V = 2491.8 (3) Å3

  • Z = 6

  • Mo K[alpha] radiation

  • [mu] = 0.09 mm-1

  • T = 103 (2) K

  • 0.42 × 0.22 × 0.18 mm
Data collection

  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.963, Tmax = 0.984

  • 27842 measured reflections

  • 4935 independent reflections

  • 4517 reflections with I > 2[sigma](I)

  • Rint = 0.034
Refinement

  • R[F2 > 2[sigma](F2)] = 0.040

  • wR(F2) = 0.101

  • S = 1.04

  • 4935 reflections

  • 203 parameters

  • H-atom parameters constrained

  • [Delta][rho]max = 0.38 e Å-3

  • [Delta][rho]min = -0.17 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
C5-H5A...O4i 1.00 2.45 3.3150 (15) 144
C7-H7A...O4i 0.99 2.55 3.4704 (16) 155
Symmetry code: (i) y+1, x, -z.

Data collection: APEX2 (Bruker, 2006[Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: APEX2; data reduction: SAINT (Bruker, 2006[Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS90 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2510 ).

Acknowledgements

RJB acknowledges the Laboratory for the Structure of Matter at the Naval Research Laboratory, Washington DC, USA, for access to their diffractometers. BN thanks Strides Arco Labs, Mangalore, India, for a gift sample of the title compound.

References

Brossi, A., Venugopalan, B., Dominguez Gerpe, L., Yeh, H. J. C., Flippen-Anderson, J. L., Buchs, P., Luo, X. D., Milhousand, W. & Peters, W. (1988). J. Med. Chem. 31, 645-650.  [CrossRef] [ChemPort] [PubMed]
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Butcher, R. J., Jasinski, J. P., Yathirajan, H. S., Bindya, S. & Narayana, B. (2007). Acta Cryst. E63, o3291-o3292.  [CSD] [CrossRef] [details]
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.  [CrossRef] [ChemPort] [ISI]
El-Feraly, F. S., Al-Yahya, M. A., Orabi, K. Y., McPhail, D. R. & McPhail, A. T. (1992). J. Nat. Prod. 55, 878-883.  [CrossRef] [ChemPort]
Flippen-Anderson, J. L., George, C., Gilardi, R., Yu, Q.-S., Dominguez, L. & Brossi, A. (1989). Acta Cryst. C45, 292-294.  [CrossRef] [details]
Grace, J. M., Aguilar, A. J., Trotman, K. M. & Brewer, T. G. (1998). Drug Metab. Dispos. 26, 313-317.  [ChemPort] [PubMed]
Jasinski, J. P., Butcher, R. J., Yathirajan, H. S., Narayana, B. & Sreevidya, T. V. (2008). Acta Cryst. E64, o89-o90.  [CrossRef] [details]
Karle, J. M. & Lin, Ai. J. (1995). Acta Cryst. B51, 1063-1068.  [CrossRef] [details]
Li, Y., Shan, F., Wu, J. M., Wu, G. S., Ding, J., Xiao, D., Yang, W. Y., Atassi, G., Leonce, S., Caignard, D. H. & Renard, P. (2001). Bioorg. Med. Chem. Lett. 11, 5-8.  [CrossRef] [PubMed]
Li, S.-H., Yue, Z.-Y., Gao, P. & Yan, P.-F. (2006). Acta Cryst. E62, o1898-o1900.  [CrossRef] [details]
Lisgarten, J., Potter, B. S., Bantuzeko, C. & Palmer, A. (1998). J. Chem. Crystallogr. 28, 539-542.  [CrossRef] [ChemPort]
Liu, X. (1980). Chin. Pharm. Bull. 15, 183-183.
Lui, J.-M., Ni, M.-Y., Fan, Y.-E., Tu, Y.-Y., Wu, Z.-H., Wu, Y.-L. & Chou, W.-S. (1979). Acta Chim. Sinica, 37, 129-141.
Luo, X. D., Yeh, H. J. C., Brossi, A., Flippen-Anderson, J. L. & Gillardi, R. (1984). Helv. Chim. Acta, 67, 1515-1522.  [CrossRef] [ChemPort]
Maggs, J. L., Bishop, L. P. D., Edwards, G., O'Neill, P. M., Ward, S. A., Winstanley, P. A. & Park, K. (2000). Drug Metab. Dispos. 28, 209-217.  [PubMed] [ChemPort]
Qinghaosu Research Group (1980). Sci. Sin. (Engl. Ed.), 23, 380-396.
Robert, A., Benoit-Vical, F., Dechy-Cabaret, O. & Meunier, B. (2001). Pure Appl. Chem. 73, 1173-1188.  [CrossRef] [ChemPort]
Saxena, S., Pant, N., Jain, D. C. & Bhakuni, R. S. (2003). Curr. Sci. 85, 1314-1329.  [ChemPort]
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Shen, C. C. & Zhuang, L. (1984). Med. Res. Rev. 4, 57-59.  [CrossRef]
Venugopalan, B., Karnik, P. J., Bapat, C. J., Chatterjee, D. K., Iyer, N. & Lepcha, D. (1995). Eur. J. Med. Chem. 30, 697-706.  [CrossRef] [ChemPort]
Wu, Y.-L. & Li, Y. (1995). Med. Chem. Res. 5, 569-586.  [ChemPort]
Wu, J. M., Shan, F., Wu, G. S., Ying, L., Ding, J., Xiao, D., Han, J.-X., Atassi, G., Leonce, S., Caignard, D. H. & Renard, P. (2001). Eur. J. Med. Chem. 36, 469-479.  [CrossRef] [PubMed] [ChemPort]
Yang, X. P., Pan, Q. C., Liang, Y.-G. & Zikang, Y.-L. (1997). Cancer, 16, 186-187.
Yue, Z.-Y., Li, S.-H., Gao, P., Zhang, J.-H. & Yan, P.-F. (2006). Acta Cryst. C62, o281-o282.  [CSD] [CrossRef] [details]

Acta Cryst (2008). E64, o585-o586   [ doi:10.1107/S1600536807062812 ]