(25R)-16β-Acet­oxy-3β-bromo-23′,26-ep­oxy-23′,25-dimethyl-5α-cholest-23,23′-en-6-one dichloro­methane monosolvate

Rincón, S.; Yépez, R.; Ochoa, M.E.; López, Y.; Santillan, R.; Farfán, N.

doi:10.1107/S1600536812043590

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 (C-C) = 0.008 Å
R = 0.068
wR = 0.181
Data-to-parameter ratio = 21.9
Details

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

Susana Rincón,^a ^* Rebeca Yépez,^b M. Eugenia Ochoa,^b Yliana López,^c Rosa Santillan ^b and Norberto Farfán ^d

^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-HO and C-HCl 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). For the use of spirostane sapogenins in the synthesis of biologically active compounds, see: Lee et al. (1976, 2009); Phillips & Shair (2007); Pettit et al. (1988). For compounds used in the sythesis and for various details of the synthetic procedure, see: Corey & Suggs (1975); Steele & Mosettig (1963); Iglesias-Arteaga et al. (1998); Monroe & Serota (1956); Rincón et al. (2006). For the crystal structure of a related steroidal compound containing bromine in the same position, see: Castro-Méndez et al. (2002). For standard bond lengths, see: Allen et al. (1987). For conformational analysis, see: Cremer & Pople (1975).

Experimental

Crystal data

C₃₁H₄₅BrO₅·CH₂Cl₂
M_r = 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 radiation
= 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(I)
R_int = 0.088

Refinement

R[F² > 2(F²)] = 0.068
wR(F²) = 0.181
S = 1.03
7934 reflections
362 parameters
H-atom parameters constrained
_max = 0.75 e Å^-3
_min = -0.68 e Å^-3
Absolute structure: Flack (1983), 3453 Friedel pairs
Flack parameter: 0.031 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
C5-H5O22ⁱ	0.98	2.54	3.491 (6)	165
C18-H18CO30ⁱⁱ	0.96	2.59	3.545 (7)	173
C27-H27BCl2ⁱⁱⁱ	0.96	2.32	2.957 (18)	124
C32-H32AO6^iv	0.97	2.23	3.00 (2)	135
C32-H32BCl1^v	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); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012).

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

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