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Volume 69 
Part 6 
Pages o879-o880  
June 2013  

Received 3 May 2013
Accepted 8 May 2013
Online 11 May 2013

Key indicators
Single-crystal X-ray study
T = 173 K
Mean [sigma](C-C) = 0.006 Å
Disorder in main residue
R = 0.063
wR = 0.185
Data-to-parameter ratio = 10.3
Details
Open access

3[beta],6[beta]-Diacetoxy-5,9[alpha]-dihydroxy-5[alpha]-cholest-7-en-11-one acetic acid 0.04-solvate

aDipartimento di Scienze Chimiche, Università degli Studi di Napoli 'Federico II', Complesso di Monte S. Angelo, Via Cinthia, 80126 Napoli, Italy
Correspondence e-mail: vinpicci@unina.it, roberto.centore@unina.it

The title compound, C31H48O7·0.04CH3COOH, is a polyoxygenated steroid obtained by selective chemical oxidation of 7-dehydrocholesteryl acetate. The asymmetric unit comprises three molecules of the steroid (Z' = 3) and a molecule of acetic acid which has occupancy factor 0.131 (5). The geometric parameters of the independent molecules do not reveal significant differences. In one molecule, the terminal isopropyl group is disordered over two sets of sites with occupancy ratio 0.869 (5):0.131 (5). The three molecules reveal different hydrogen-bonding patterns. Each of them is involved in an intramolecular S(6) hydrogen-bonding motif, involving hydroxy groups as donor and acceptor. In the crystal, two independent molecules form dimers through hydrogen bonding between an OH donor and an acetate carbonyl acceptor, giving rise to R22(16) ring patterns. A single hydrogen bond between the OH group and a ketone carbonyl group is observed between two symmetry-independent molecules.

Related literature

For general information on the isolation of polyoxygenated steroids from marine source, see: Piccialli & Sica (1986[Piccialli, V. & Sica, D. (1986). J. Nat. Prod. 49, 779-783.], 1987[Piccialli, V. & Sica, D. (1987). J. Nat. Prod. 50, 915-920.]); Migliuolo et al. (1990[Migliuolo, A., Notaro, G., Piccialli, V. & Sica, D. (1990). J. Nat. Prod. 53, 1414-1424.]); Notaro et al. (1991[Notaro, G., Piccialli, V., Sica, D. & Corriero, G. (1991). J. Nat. Prod. 54, 1570-1575.], 1992[Notaro, G., Piccialli, V., Sica, D. & Pronzato, R. (1992). J. Nat. Prod. 55, 773-779.]). For the synthesis of polyoxygenated steroids, see: Madaio et al. (1988[Madaio, A., Piccialli, V. & Sica, D. (1988). Tetrahedron Lett. 29, 5999-6000.]); Migliuolo et al. (1992[Migliuolo, A., Piccialli, V. & Sica, D. (1992). Steroids, 57, 344-347.]). For new selective oxidation protocols, see: Piccialli et al. (1993[Piccialli, V., Smaldone, D. M. A. & Sica, D. (1993). Tetrahedron, 49, 4211-4228.], 2013[Piccialli, V., D'Errico, S., Borbone, N., Oliviero, G., Centore, R. & Zaccaria, S. (2013). Eur. J. Org. Chem. pp. 1781-1789.]); Notaro et al. (1994[Notaro, G., Piccialli, V., Sica, D. & Smaldone, D. M. A. (1994). Tetrahedron, 50, 4835-4852.]); Bifulco et al. (2003[Bifulco, G., Caserta, T., Gomez-Paloma, L. & Piccialli, V. (2003). Tetrahedron Lett. 44, 5499-5503.]); Caserta et al. (2005[Caserta, T., Piccialli, V., Gomez-Paloma, L. & Bifulco, G. (2005). Tetrahedron, 61, 927-939.]). For the cytotoxic activity of polyoxygenated steroids, see: Chen et al. (2011[Chen, B.-W., Chang, S.-M., Huang, C.-Y., Su, J.-H., Wen, Z.-H., Wu, Y.-C. & Sheu, J.-H. (2011). Org. Biomol. Chem. 9, 3272-3278.]). For a general survey of hydrogen bonding and hydrogen-bonding synthons in crystals, see: Allen et al. (1999[Allen, F. H., Motherwell, W. D. S., Raithby, P. R., Shields, G. P. & Taylor, R. (1999). New J. Chem. pp. 25-34.]); Steiner (2002[Steiner, T. (2002). Angew. Chem. Int. Ed. 41, 48-76.]). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). For recent examples of hydrogen bonding in crystals, see: Centore, Fusco, Jazbinsek et al. (2013[Centore, R., Fusco, S., Jazbinsek, M., Capobianco, A. & Peluso, A. (2013). CrystEngComm, 15, 3318-3325.]); Centore et al. (2013a[Centore, R., Piccialli, V. & Tuzi, A. (2013a). Acta Cryst. E69, o667-o668.],b[Centore, R., Piccialli, V. & Tuzi, A. (2013b). Acta Cryst. E69, o802-o803.]); Centore, Fusco, Capobianco et al. (2013[Centore, R., Fusco, S., Capobianco, A., Piccialli, V., Zaccaria, S. & Peluso, A. (2013). Eur. J. Org. Chem. doi:10.1002/ejoc.201201653.]). For the presence of multiple molecules in the asymmetric unit, see: Desiraju (2007[Desiraju, G. R. (2007). CrystEngComm, 9, 91-92.]).

[Scheme 1]

Experimental

Crystal data
  • C31H48O7·0.04C2H4O2

  • Mr = 535.45

  • Orthorhombic, P 21 21 21

  • a = 10.242 (2) Å

  • b = 28.556 (5) Å

  • c = 30.214 (6) Å

  • V = 8837 (3) Å3

  • Z = 12

  • Mo K[alpha] radiation

  • [mu] = 0.08 mm-1

  • T = 173 K

  • 0.45 × 0.30 × 0.17 mm

Data collection
  • Bruker-Nonius KappaCCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.963, Tmax = 0.986

  • 82574 measured reflections

  • 11048 independent reflections

  • 6969 reflections with I > 2[sigma](I)

  • Rint = 0.097

Refinement
  • R[F2 > 2[sigma](F2)] = 0.063

  • wR(F2) = 0.185

  • S = 1.00

  • 11048 reflections

  • 1072 parameters

  • 13 restraints

  • H-atom parameters constrained

  • [Delta][rho]max = 0.29 e Å-3

  • [Delta][rho]min = -0.31 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
O1A-H1AO...O3Ci 0.95 1.79 2.745 (4) 177
O1B-H1BO...O5C 0.80 2.02 2.819 (4) 175
O1C-H1CO...O5B 0.89 1.81 2.699 (4) 178
O2A-H2AO...O1A 0.93 1.88 2.691 (4) 145
O2B-H2BO...O1B 0.90 1.80 2.628 (4) 153
O2C-H2CO...O1C 1.05 1.77 2.614 (4) 134
Symmetry code: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: COLLECT (Nonius, 1999[Nonius, B. V. (1999). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000[Duisenberg, A. J. M., Hooft, R. W. W., Schreurs, A. M. M. & Kroon, J. (2000). J. Appl. Cryst. 33, 893-898.]); data reduction: EVALCCD (Duisenberg et al., 2003[Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003). J. Appl. Cryst. 36, 220-229.]); program(s) used to solve structure: SIR97 (Altomare et al., 1999[Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115-119.]); 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, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]); 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: KP2452 ).


Acknowledgements

The authors thank the Centro Interdipartimentale di Metodologie Chimico-Fisiche, Università degli Studi di Napoli "Federico II" for the X-ray facilities.

References

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Caserta, T., Piccialli, V., Gomez-Paloma, L. & Bifulco, G. (2005). Tetrahedron, 61, 927-939.  [ISI] [CrossRef] [ChemPort]
Centore, R., Fusco, S., Capobianco, A., Piccialli, V., Zaccaria, S. & Peluso, A. (2013). Eur. J. Org. Chem. doi:10.1002/ejoc.201201653.
Centore, R., Fusco, S., Jazbinsek, M., Capobianco, A. & Peluso, A. (2013). CrystEngComm, 15, 3318-3325.  [ISI] [CSD] [CrossRef] [ChemPort]
Centore, R., Piccialli, V. & Tuzi, A. (2013a). Acta Cryst. E69, o667-o668.  [CrossRef] [ChemPort] [details]
Centore, R., Piccialli, V. & Tuzi, A. (2013b). Acta Cryst. E69, o802-o803.  [CrossRef] [ChemPort] [details]
Chen, B.-W., Chang, S.-M., Huang, C.-Y., Su, J.-H., Wen, Z.-H., Wu, Y.-C. & Sheu, J.-H. (2011). Org. Biomol. Chem. 9, 3272-3278.  [CrossRef] [ChemPort] [PubMed]
Desiraju, G. R. (2007). CrystEngComm, 9, 91-92.  [ISI] [CrossRef] [ChemPort]
Duisenberg, A. J. M., Hooft, R. W. W., Schreurs, A. M. M. & Kroon, J. (2000). J. Appl. Cryst. 33, 893-898.  [ISI] [CrossRef] [ChemPort] [details]
Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003). J. Appl. Cryst. 36, 220-229.  [ISI] [CrossRef] [ChemPort] [details]
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.  [ISI] [CrossRef] [ChemPort] [details]
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.  [ISI] [CrossRef] [ChemPort] [details]
Madaio, A., Piccialli, V. & Sica, D. (1988). Tetrahedron Lett. 29, 5999-6000.  [CrossRef] [ChemPort] [ISI]
Migliuolo, A., Notaro, G., Piccialli, V. & Sica, D. (1990). J. Nat. Prod. 53, 1414-1424.  [CrossRef] [ChemPort] [ISI]
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Notaro, G., Piccialli, V., Sica, D. & Pronzato, R. (1992). J. Nat. Prod. 55, 773-779.  [CrossRef] [ISI]
Notaro, G., Piccialli, V., Sica, D. & Smaldone, D. M. A. (1994). Tetrahedron, 50, 4835-4852.  [CrossRef] [ChemPort] [ISI]
Piccialli, V., D'Errico, S., Borbone, N., Oliviero, G., Centore, R. & Zaccaria, S. (2013). Eur. J. Org. Chem. pp. 1781-1789.  [CSD] [CrossRef]
Piccialli, V. & Sica, D. (1986). J. Nat. Prod. 49, 779-783.  [CrossRef] [ChemPort] [ISI]
Piccialli, V. & Sica, D. (1987). J. Nat. Prod. 50, 915-920.  [CrossRef] [ChemPort] [ISI]
Piccialli, V., Smaldone, D. M. A. & Sica, D. (1993). Tetrahedron, 49, 4211-4228.  [CrossRef] [ChemPort] [ISI]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [ChemPort] [details]
Steiner, T. (2002). Angew. Chem. Int. Ed. 41, 48-76.  [ISI] [CrossRef] [ChemPort]


Acta Cryst (2013). E69, o879-o880   [ doi:10.1107/S1600536813012646 ]

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