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Volume 68 
Part 11 
Pages o3222-o3223  
November 2012  

Received 19 October 2012
Accepted 22 October 2012
Online 27 October 2012

Key indicators
Single-crystal X-ray study
T = 90 K
Mean [sigma](C-C) = 0.002 Å
R = 0.028
wR = 0.074
Data-to-parameter ratio = 15.0
Details
Open access

Redetermination and absolute configuration of (+)-7-epiclusianone

aDepartment of Chemistry, McNeese State University, Lake Charles, LA 70609, USA,bDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804, USA, and cLouisiana Environmental Research Center, McNeese State University, Lake Charles, LA 70609, USA
Correspondence e-mail: ochristian@mcneese.edu

The absolute configuration of 3-benzoyl-4-hydroxy-6,6-dimethyl-1,5,7-tris(3-methylbut-2-enyl)bicyclo[3.3.1]non-3-ene-2,9-dione, C33H42O4, isolated from Hypericum hypericoides, has been determined. The previous study [Xiao et al. (2007[Xiao, Z. Y., Mu, Q., Shiu, W. K. P., Zeng, Y. H. & Gibbons, S. (2007). J. Nat. Prod. 70, 1779-1782.]). J. Nat. Prod. 70, 1779-1782] gave only the established relative configuration. The three stereogenic centers are now established as 1R, 5R and 7S on the basis of the refinement of the Flack absolute structure parameter against Cu K[alpha] data and correspond to a specific rotation of [[alpha]]D20 = +66°. The enol-hydroxy group forms an intramolecular O-H...O hydrogen bond to close an S(6) ring.

Related literature

For a review of polycyclic polyprenylated acylphloroglucinols, see: Ciochina & Grossman (2006[Ciochina, R. & Grossman, R. B. (2006). Chem. Rev. 106, 3963-3986.]). For background to Clusiaceae metabolites, see: Garnsey et al. (2011[Garnsey, M. R., Matous, J. A., Kwiek, J. J. & Coltart, D. M. (2011). Bioorg. Med. Chem. Lett. 21, 2406-2409.]); Zhang et al. (2010[Zhang, Q., Mitasev, B., Qi, J. & Proco, J. A. Jr (2010). J. Am. Chem. Soc. 132, 14212-14215.]); Christian et al. (2008[Christian, O. E., McLean, S., Reynolds, W. F. & Jacobs, H. (2008). Nat. Prod. Commun. 3, 1781-1786.]); Wu et al. (2008[Wu, C.-C., Yen, M.-Y., Yang, S.-C. & Lin, C.-N. (2008). J. Nat. Prod. 71, 1027-1031.]). For relative-configuration structure determinatons, see: Santos et al. (1998[Santos, M. H., Speziali, N. L., Nagem, T. J. & Oliveira, T. T. (1998). Acta Cryst. C54, 1990-1992.]); Xiao et al. (2007[Xiao, Z. Y., Mu, Q., Shiu, W. K. P., Zeng, Y. H. & Gibbons, S. (2007). J. Nat. Prod. 70, 1779-1782.]); Martins et al. (2009[Martins, F. T., Assis, D. M., dos Santos, M. H., Camps, I., Veloso, M. P., Juliano, M. A., Alves, L. C. & Doriguetto, A. C. (2009). Eur. J. Med. Chem. 44, 1230-1239.]). For related structures, see: McCandlish et al. (1976[McCandlish, L. E., Hanson, J. C. & Stout, G. H. (1976). Acta Cryst. B32, 1793-1801.]); Fronczek et al. (2012[Fronczek, F. R., Christian, O. & Crockett, S. (2012). ACA Annual Meeting, Boston, MA, USA. Abstract S-81.]). For optical rotation results for the title compound, see: Piccinelli et al. (2005[Piccinelli, A. L., Cuesta-Rubio, O., Chica, M. B., Mahmood, N., Pagano, B., Pavone, M., Barone, V. & Rastrelli, L. (2005). Tetrahedron, 61, 8206-8211.]) and for related compounds, see: Tanaka et al. (2004[Tanaka, N., Takaishi, Y., Shikishima, Y., Nakanishi, Y., Bastow, K., Lee, K.-H., Honda, G., Ito, M., Takeda, Y., Kodzhimatov, O. K. & Ashurmetov, O. (2004). J. Nat. Prod. 67, 1870-1875.]). For keto-enol tautomerism in related compounds, see: Martins et al. (2007[Martins, F. T., Cruz, J. W. Jr, Derogis, B. M. C., dos Santos, M. H., Veloso, M. P., Ellena, J. & Doriguetto, A. C. (2007). J. Braz. Chem. Soc. 18, 1515-1523.]). For absolute configuration based on resonant scattering from light atoms, see: Hooft et al. (2008[Hooft, R. W. W., Straver, L. H. & Spek, A. L. (2008). J. Appl. Cryst. 41, 96-103.])

[Scheme 1]

Experimental

Crystal data
  • C33H42O4

  • Mr = 502.67

  • Orthorhombic, P 21 21 21

  • a = 8.6177 (4) Å

  • b = 12.4157 (6) Å

  • c = 26.8632 (13) Å

  • V = 2874.2 (2) Å3

  • Z = 4

  • Cu K[alpha] radiation

  • [mu] = 0.59 mm-1

  • T = 90 K

  • 0.25 × 0.24 × 0.16 mm

Data collection
  • Bruker Kappa APEXII CCD DUO diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004[Sheldrick, G. (2004). SADABS. University of Göttingen, Germany.]) Tmin = 0.824, Tmax = 0.889

  • 17192 measured reflections

  • 5171 independent reflections

  • 5131 reflections with I > 2[sigma](I)

  • Rint = 0.029

Refinement
  • R[F2 > 2[sigma](F2)] = 0.028

  • wR(F2) = 0.074

  • S = 1.03

  • 5171 reflections

  • 345 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • [Delta][rho]max = 0.22 e Å-3

  • [Delta][rho]min = -0.14 e Å-3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 2200 Friedel pairs

  • Flack parameter: 0.04 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
O2-H2O...O4 1.014 (16) 1.477 (16) 2.4368 (12) 155.7 (15)

Data collection: APEX2 (Bruker, 2006[Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2006[Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (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: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB6978 ).


Acknowledgements

Financial support provided by the Louisiana Environmental Research Center (LERC), Chenier Plain Sustainability Initiative Collaboration Award # 687217-10-006. Upgrade of the diffractometer was made possible by grant No. LEQSF(2011-12)-ENH-TR-01, administered by the Louisiana Board of Regents.

References

Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
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Ciochina, R. & Grossman, R. B. (2006). Chem. Rev. 106, 3963-3986.  [ISI] [CrossRef] [PubMed] [ChemPort]
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  [CrossRef] [details]
Flack, H. D. (1983). Acta Cryst. A39, 876-881.  [CrossRef] [details]
Fronczek, F. R., Christian, O. & Crockett, S. (2012). ACA Annual Meeting, Boston, MA, USA. Abstract S-81.
Garnsey, M. R., Matous, J. A., Kwiek, J. J. & Coltart, D. M. (2011). Bioorg. Med. Chem. Lett. 21, 2406-2409.  [CrossRef] [ChemPort] [PubMed]
Hooft, R. W. W., Straver, L. H. & Spek, A. L. (2008). J. Appl. Cryst. 41, 96-103.  [ISI] [CrossRef] [ChemPort] [details]
Martins, F. T., Assis, D. M., dos Santos, M. H., Camps, I., Veloso, M. P., Juliano, M. A., Alves, L. C. & Doriguetto, A. C. (2009). Eur. J. Med. Chem. 44, 1230-1239.  [ISI] [CSD] [CrossRef] [PubMed] [ChemPort]
Martins, F. T., Cruz, J. W. Jr, Derogis, B. M. C., dos Santos, M. H., Veloso, M. P., Ellena, J. & Doriguetto, A. C. (2007). J. Braz. Chem. Soc. 18, 1515-1523.  [CrossRef] [ChemPort]
McCandlish, L. E., Hanson, J. C. & Stout, G. H. (1976). Acta Cryst. B32, 1793-1801.  [CrossRef] [details] [ISI]
Piccinelli, A. L., Cuesta-Rubio, O., Chica, M. B., Mahmood, N., Pagano, B., Pavone, M., Barone, V. & Rastrelli, L. (2005). Tetrahedron, 61, 8206-8211.  [ISI] [CrossRef] [ChemPort]
Santos, M. H., Speziali, N. L., Nagem, T. J. & Oliveira, T. T. (1998). Acta Cryst. C54, 1990-1992.  [CSD] [CrossRef] [details]
Sheldrick, G. (2004). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Tanaka, N., Takaishi, Y., Shikishima, Y., Nakanishi, Y., Bastow, K., Lee, K.-H., Honda, G., Ito, M., Takeda, Y., Kodzhimatov, O. K. & Ashurmetov, O. (2004). J. Nat. Prod. 67, 1870-1875.  [ISI] [CrossRef] [PubMed] [ChemPort]
Wu, C.-C., Yen, M.-Y., Yang, S.-C. & Lin, C.-N. (2008). J. Nat. Prod. 71, 1027-1031.  [ISI] [CrossRef] [PubMed] [ChemPort]
Xiao, Z. Y., Mu, Q., Shiu, W. K. P., Zeng, Y. H. & Gibbons, S. (2007). J. Nat. Prod. 70, 1779-1782.  [ISI] [CSD] [CrossRef] [PubMed] [ChemPort]
Zhang, Q., Mitasev, B., Qi, J. & Proco, J. A. Jr (2010). J. Am. Chem. Soc. 132, 14212-14215.  [ISI] [CSD] [CrossRef] [ChemPort] [PubMed]


Acta Cryst (2012). E68, o3222-o3223   [ doi:10.1107/S1600536812043784 ]

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