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Volume 68 
Part 12 
Pages o3260-o3261  
December 2012  

Received 14 October 2012
Accepted 21 October 2012
Online 3 November 2012

Key indicators
Single-crystal X-ray study
T = 293 K
Mean [sigma](C-C) = 0.008 Å
R = 0.068
wR = 0.181
Data-to-parameter ratio = 21.9
Details
Open access

(25R)-16[beta]-Acetoxy-3[beta]-bromo-23',26-epoxy-23',25-dimethyl-5[alpha]-cholest-23,23'-en-6-one dichloromethane monosolvate

aDivisión de Posgrado, Instituto Tecnológico de Mérida, Avenida Tecnológico, Km 4.5 S/N C.P. 97118, Mérida Yucatán, Mexico,bDepartamento de Química, CINVESTAV-IPN, Apdo. Postal 14-740, 07000 México, D.F., Mexico,cInstituto de Investigaciones Químico-Biológicas, Universidad Michoacana de San Nicolás de Hidalgo, Morelia, Michoacán, C.P. 58000, Mexico, and dFacultad de Química, Departamento de Química Orgánica, Universidad Nacional Autónoma de México, México D.F., 04510, Mexico
Correspondence e-mail: susana74a@yahoo.com

The crystal structure of the title compound, C31H45BrO5·CH2Cl2, prepared in six steps from diosgenin, confirmed that the configurations of the stereogenic centers, positions 20S and 25R, remain unchanged during the reaction. The six-membered A, B and C rings have chair conformations. The five-membered ring D has an envelope conformation (with the methyl-substituted C atom fused to ring C as the flap) and the six-membered dihydropyran ring E adopts a twist-boat conformation. In the crystal, molecules are linked via C-H...O and C-H...Cl hydrogen bonds, the latter involving the dichloromethane solvent molecule, forming a three-dimensional supramolecular network.

Related literature

For a review on saponins, see: Hostettmann & Marston (1995[Hostettmann, K. & Marston, A. (1995). Saponins. Cambridge University Presss.]). For the use of spirostane sapogenins in the synthesis of biologically active compounds, see: Lee et al. (1976[Lee, E., Liu, Y. T., Solomon, P. H. & Nakanishi, K. (1976). J. Am. Chem. Soc. 98, 1634-1635.], 2009[Lee, S., LaCour, T. G. & Fuchs, P. L. (2009). Chem. Rev. 109, 2275-2314.]); Phillips & Shair (2007[Phillips, S. T. & Shair, M. D. (2007). J. Am. Chem. Soc. 129, 6589-6598.]); Pettit et al. (1988[Pettit, G. R., Inoue, M., Kamano, Y., Herald, D. L., Arm, C., Dufresne, C., Christie, N. D., Schmidt, J. M., Doubek, D. L. & Krupa, T. S. (1988). J. Am. Chem. Soc. 110, 2006-2007.]). For compounds used in the sythesis and for various details of the synthetic procedure, see: Corey & Suggs (1975[Corey, E. J. & Suggs, J. W. (1975). Tetrahedron Lett. 16, 2647-2650.]); Steele & Mosettig (1963[Steele, J. A. & Mosettig, E. (1963). J. Org. Chem. 28, 571-572.]); Iglesias-Arteaga et al. (1998[Iglesias-Arteaga, M. A., Pérez Gil, R., Leliebre Lara, V., Coll Manchado, F. & Pérez Martínez, C. S. (1998). Synth. Commun. 28, 75-81.]); Monroe & Serota (1956[Monroe, E. W. & Serota, S. (1956). J. Am. Chem. Soc. 78, 1747-1750.]); Rincón et al. (2006[Rincón, S., del Río, R. E., Sandoval-Ramírez, J., Meza-Reyes, S., Montiel-Smith, S., Fernández, M. A., Farfán, N. & Santillan, R. (2006). Tetrahedron, 62, 2594-2602.]). For the crystal structure of a related steroidal compound containing bromine in the same position, see: Castro-Méndez et al. (2002[Castro-Méndez, A., Sandoval-Ramírez, J. & Bernès, S. (2002). Acta Cryst. E58, o606-o608.]). For standard bond lengths, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2. pp. S1-19.]). For conformational analysis, see: Cremer & Pople (1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]).

[Scheme 1]

Experimental

Crystal data
  • C31H45BrO5·CH2Cl2

  • Mr = 662.51

  • Orthorhombic, P 21 21 21

  • a = 7.4423 (1) Å

  • b = 15.6578 (2) Å

  • c = 26.8496 (3) Å

  • V = 3128.79 (7) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 1.52 mm-1

  • T = 293 K

  • 0.15 × 0.10 × 0.08 mm

Data collection
  • Nonius KappaCCD diffractometer

  • 37310 measured reflections

  • 7934 independent reflections

  • 5668 reflections with I > 2[sigma](I)

  • Rint = 0.088

Refinement
  • R[F2 > 2[sigma](F2)] = 0.068

  • wR(F2) = 0.181

  • S = 1.03

  • 7934 reflections

  • 362 parameters

  • H-atom parameters constrained

  • [Delta][rho]max = 0.75 e Å-3

  • [Delta][rho]min = -0.68 e Å-3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 3453 Friedel pairs

  • Flack parameter: 0.031 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
C5-H5...O22i 0.98 2.54 3.491 (6) 165
C18-H18C...O30ii 0.96 2.59 3.545 (7) 173
C27-H27B...Cl2iii 0.96 2.32 2.957 (18) 124
C32-H32A...O6iv 0.97 2.23 3.00 (2) 135
C32-H32B...Cl1v 0.97 2.16 2.89 (3) 130
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) x+1, y, z; (iii) [-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iv) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (v) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z].

Data collection: COLLECT (Nonius, 1999[Nonius (1999). KappaCCD Server Software. Nonius BV, Delft, The Netherlands.]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and SCALEPACK; 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: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]).


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SU2514 ).


Acknowledgements

The authors thank CONACYT for financial support and the Consejo Superior de la Investigación Científica in Spain for the award of a license for the use of the Cambridge Structural Database. Thanks are due to Marco A. Leyva-Ramírez (CINVESTAV-IPN) for helpful discussions.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2. pp. S1-19.
Castro-Méndez, A., Sandoval-Ramírez, J. & Bernès, S. (2002). Acta Cryst. E58, o606-o608.  [CSD] [CrossRef] [details]
Corey, E. J. & Suggs, J. W. (1975). Tetrahedron Lett. 16, 2647-2650.  [CrossRef]
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.  [CrossRef] [ChemPort] [ISI]
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.  [ISI] [CrossRef] [ChemPort] [details]
Flack, H. D. (1983). Acta Cryst. A39, 876-881.  [CrossRef] [details]
Hostettmann, K. & Marston, A. (1995). Saponins. Cambridge University Presss.
Iglesias-Arteaga, M. A., Pérez Gil, R., Leliebre Lara, V., Coll Manchado, F. & Pérez Martínez, C. S. (1998). Synth. Commun. 28, 75-81.  [ISI] [CrossRef]
Lee, S., LaCour, T. G. & Fuchs, P. L. (2009). Chem. Rev. 109, 2275-2314.  [ISI] [CrossRef] [PubMed] [ChemPort]
Lee, E., Liu, Y. T., Solomon, P. H. & Nakanishi, K. (1976). J. Am. Chem. Soc. 98, 1634-1635.  [CrossRef] [PubMed] [ChemPort] [ISI]
Monroe, E. W. & Serota, S. (1956). J. Am. Chem. Soc. 78, 1747-1750.
Nonius (1999). KappaCCD Server Software. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.
Pettit, G. R., Inoue, M., Kamano, Y., Herald, D. L., Arm, C., Dufresne, C., Christie, N. D., Schmidt, J. M., Doubek, D. L. & Krupa, T. S. (1988). J. Am. Chem. Soc. 110, 2006-2007.  [CrossRef] [ChemPort] [ISI]
Phillips, S. T. & Shair, M. D. (2007). J. Am. Chem. Soc. 129, 6589-6598.  [ISI] [CSD] [CrossRef] [PubMed] [ChemPort]
Rincón, S., del Río, R. E., Sandoval-Ramírez, J., Meza-Reyes, S., Montiel-Smith, S., Fernández, M. A., Farfán, N. & Santillan, R. (2006). Tetrahedron, 62, 2594-2602.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Spek, A. L. (2009). Acta Cryst. D65, 148-155.  [ISI] [CrossRef] [details]
Steele, J. A. & Mosettig, E. (1963). J. Org. Chem. 28, 571-572.  [CrossRef] [ChemPort]


Acta Cryst (2012). E68, o3260-o3261   [ doi:10.1107/S1600536812043590 ]

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