3β-Chloro-5α-cholestan-6-one

Samina Khan Yusufzai; Hasnah Osman; Aisyah Saad Abdul Rahim; Suhana Arshad; Ibrahim Abdul Razak

doi:10.1107/S1600536812012482

. 2012 Mar 28;68(Pt 4):o1211–o1212. doi: 10.1107/S1600536812012482

3β-Chloro-5α-cholestan-6-one

Samina Khan Yusufzai ^a, Hasnah Osman ^a,^‡, Aisyah Saad Abdul Rahim ^b, Suhana Arshad ^c, Ibrahim Abdul Razak ^c,^*,^§

PMCID: PMC3344147 PMID: 22606150

Abstract

The asymmetric unit of the title compound, C₂₇H₄₅ClO, consists of two crystallographically independent molecules. In both molecules, the three cyclohexane rings in the steroid fused-ring systems adopt chair conformations, while the cyclopentane ring adopts a half-chair conformation in one molecule and an envelope conformation in the other. In the crystal, the molecules are linked into a two-dimensional network by weak C—H⋯O hydrogen bonds. The crystal studied is a nonmerohedral twin with a refined ratio of twin components of 0.264 (3):0.736 (3).

Related literature

For a crystallographic comparison of cholesterols, see: Rajnikant et al. (2006 ▶). For the biological activity of steroidal derivatives, see: Pluempe & Pulls (1971 ▶); Sawhney et al. (1975 ▶); Yonova & Stoilkova (2004 ▶). For related structures, see: Yusufzai et al. (2012 ▶); Ketuly et al. (2011 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For the synthesis, see: Windaus & Dalmer (1919 ▶). For the stability of the temperature controller used for data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₇H₄₅ClO
M _r = 421.08
Monoclinic,
a = 7.6603 (3) Å
b = 15.7249 (6) Å
c = 20.8434 (8) Å
β = 94.069 (2)°
V = 2504.41 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 100 K
0.25 × 0.18 × 0.14 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.960, T _max = 0.977
14186 measured reflections
14186 independent reflections
10360 reflections with I > 2σ(I)
R _int = 0.000

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.179
S = 1.02
14186 reflections
534 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.34 e Å⁻³
Absolute structure: Flack (1983 ▶), 6535 Friedel pairs
Flack parameter: 0.03 (6)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812012482/lh5434sup1.cif

e-68-o1211-sup1.cif^{(59.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812012482/lh5434Isup2.hkl

e-68-o1211-Isup2.hkl^{(693.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7A—H7AA⋯O1Aⁱ	0.99	2.37	3.349 (4)	168
C7B—H7BA⋯O1Bⁱ	0.99	2.47	3.265 (4)	137
C23A—H23B⋯O1Bⁱⁱ	0.99	2.51	3.414 (4)	152
C23B—H23D⋯O1Aⁱⁱⁱ	0.99	2.50	3.453 (4)	161

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for the FRGS grant (No. 203/PKIMIA/6711179), MOSTI grant No. 09-05-lfn-meb-004 and Research University grant No.1001/PFIZIK/811151 to conduct this work. SKY thanks USM for providing Graduate Assistance financial support.

supplementary crystallographic information

Comment

The cholesterol molecule in steroidal chemistry is well known as it comprises of a four-ring structure of which three are six-membered cyclohexane rings and one is a five membered carbon ring (Rajnikant et al., 2006). The importance of steroidal compounds has long been recognized in the field of synthetic organic chemistry and steroidal derivatives are an important group of natural compounds possessing a variety of biological activities such as antidiabetic, bactericidal, fungicidal, herbicidal and algeacidal activities (Pluempe & Pulls, 1971; Sawhney et al., 1975; Yonova & Stoilkova, 2004). In the present work an attempt has been made to synthesize a derivative of the cholesterol molecule. The crystal structure of the title compound is presented herein.

The asymmetric unit of the title compound (Fig. 1), consists of two crystallographically independent molecules A and B. The bond lengths and angles are within normal ranges and are comparable to the related structures (Yusufzai et al., 2012; Ketuly et al., 2011). In molecule A, the cyclohexane (C1A–C3A/C8A/C9A/C17A, C3A–C8A & C9A–C12A/C16A/C17A) rings adopt chair conformation (Cremer & Pople, 1975) [puckering parameters Q= 0.560 (3) Å, Θ= 169.0 (3)° and Φ= 353.7 (15)°; Q= 0.571 (3) Å, Θ= 180.0 (3)° and Φ= 283.0 (17)° and Q= 0.577 (3) Å, Θ= 173.9 (3)° and Φ= 54.0 (3)°, respectively] while the cyclopentane (C12A–C16A) ring is twisted about the C16A—C12A bond [puckering parameters Q= 0.452 (3) Å and φ= 349.1 (4)°], thereby adopting a half-chair conformation. Meanwhile, in molecule B, the cyclohexane (C1B–C3B/C8B/C9B/C17B, C3B–C8B & C9B–C12B/C16B/C17B) rings adopt chair conformations [puckering parameters Q= 0.562 (3) Å, Θ= 167.4 (3)° and Φ= 352.5 (14)°; Q= 0.564 (3) Å, Θ= 178.4 (3)° and Φ= 298.0 (8)° and Q= 0.569 (3) Å, Θ= 175.7 (3)° and Φ= 52.0 (4)°, respectively] and the cyclopentane (C12B–C16B) ring is in envelope conformation with puckering parameters Q= 0.456 (3) Å and φ= 351.4 (4)° with atom C12B at the flap.

There are nine chiral centres presented in each molecule. From the structure presented, these centers exhibit the following relative chiralities: C3A/C3B = S; C5A/C5B = S; C8A/C8B = R; C9A/C9B = S; C12A/C12B = R; C13A/C13B = R; C16A/C16B = S; C17A/C17B = S and C21A/C21B = R.

The crystal packing is shown in Fig. 2. The molecules are connected by C7A—H7AA···O1Aⁱ, C7B—H7BA···O1Bⁱ6, C23A—H23B···O1Bⁱⁱ and C23B—H23D···O1Aⁱⁱⁱ intermolecular hydrogen bonds (Table 1) into a two-dimensional network parallel to ac plane.

Experimental

A solution of 3β-chloro-6-nitrocholest-5-ene (12 g) and glacial acetic acid (240 ml) was heated just to get a clear solution. Then zinc dust (24 g) was added gradually in small portions with constant shaking. The suspension was heated under reflux for 4 h and water (24 ml) was added at regular intervals during the course of reaction. The hot solution was poured into ice-cold water. The organic matter was extracted with ether and ethereal solution was washed successively with water, sodium bicarbonate solution (5%) and again with water and dried over anhydrous sodium sulfate. Evaporation of the solvent furnished the ketone as an oil which was crystallized from methanol to give shiny needle like crystals, m.p.: 401-402K [reported m.p. 402K (Windaus & Dalmer, 1919)].