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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1124.
Published online 2009 April 25. doi:  10.1107/S1600536809014585
PMCID: PMC2977798

(20R)-24-Bromo-5β-cholane

Abstract

In the title compound (5S,8R,9R,10R,13S,14S,17R,20R)-24-bromo-5β-cholane, C24H41Br, the fused-chair conformation of the cyclo­hexane A/B ring junction is cis with a 5β-H configuration.

Related literature

For the isostructural chloro analog, see: Cox et al. (2001 [triangle]).

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Object name is e-65-o1124-scheme1.jpg

Experimental

Crystal data

  • C24H41Br
  • M r = 409.48
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1124-efi1.jpg
  • a = 7.4797 (2) Å
  • b = 9.9094 (3) Å
  • c = 29.3371 (8) Å
  • V = 2174.5 (1) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.90 mm−1
  • T = 100 K
  • 0.30 × 0.10 × 0.03 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.606, T max = 0.746 (expected range = 0.767–0.945)
  • 15233 measured reflections
  • 4988 independent reflections
  • 4263 reflections with I > 2σ(I)
  • R int = 0.048

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.075
  • S = 0.99
  • 4988 reflections
  • 226 parameters
  • H-atom parameters constrained
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.28 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 2124 Friedel pairs
  • Flack parameter: 0.018 (8)

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809014585/tk2433sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014585/tk2433Isup2.hkl

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

Acknowledgments

We are grateful to the late Professor Charles J. W. Brooks of Glasgow University for the gift of 24-hydroxy-5β-cholane. We thank the University of Malaya for supporting this study.

supplementary crystallographic information

Experimental

The procedure employed was that used for synthesizing 5β-cholan-24-yl chloride, but with phosphorus tribromide in place of phosphorus trichloride. Phosphorus tribromide (0.06 ml, 0.65 mmol) in dichloromethane (10 ml) was added to 24-hydroxy-5β-cholane (22 mg, 0.65 mmol) in dichloromethane (10 ml). The mixture was kept at 283–288 K under stirring for 12 h and then made basic with sodium bicarbonate solution. The organic compound was extracted with hexane–ethyl acetate (4:1 v/v). The solvent was removed to give a yellow oil, which gradually solidified (135 mg). The compound was dissolved in hexane and chromatographed on silica gel (10 g). The first fraction gave the pure compound, m.p. 335–338 K, when the solvent was allowed to evaporate.

Refinement

Hydrogen atoms were placed at calculated positions (C–H 0.98–1.00 Å) and were treated as riding on their parent carbon atoms, with U(H) set to 1.2–1.5 times Ueq(C).

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of C24H41Br at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C24H41BrF(000) = 880
Mr = 409.48Dx = 1.251 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3210 reflections
a = 7.4797 (2) Åθ = 2.8–24.5°
b = 9.9094 (3) ŵ = 1.90 mm1
c = 29.3371 (8) ÅT = 100 K
V = 2174.5 (1) Å3Plate, colorless
Z = 40.30 × 0.10 × 0.03 mm

Data collection

Bruker SMART APEX diffractometer4988 independent reflections
Radiation source: fine-focus sealed tube4263 reflections with I > 2σ(I)
graphiteRint = 0.048
ω scansθmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −9→9
Tmin = 0.606, Tmax = 0.746k = −12→12
15233 measured reflectionsl = −37→38

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.075w = 1/[σ2(Fo2) + (0.0372P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.001
4988 reflectionsΔρmax = 0.33 e Å3
226 parametersΔρmin = −0.28 e Å3
0 restraintsAbsolute structure: Flack (1983), 2124 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.018 (8)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Br10.12174 (4)0.77061 (3)−0.054189 (9)0.02429 (8)
C10.0806 (4)0.6772 (3)0.00361 (9)0.0224 (6)
H1A0.11650.73700.02900.027*
H1B−0.04870.65810.00690.027*
C20.1835 (4)0.5463 (3)0.00693 (9)0.0177 (6)
H2A0.31330.56580.00790.021*
H2B0.15940.4906−0.02040.021*
C30.1301 (4)0.4678 (2)0.04965 (8)0.0193 (5)
H3A−0.00020.45050.04860.023*
H3B0.15430.52460.07670.023*
C40.2281 (3)0.3324 (2)0.05535 (10)0.0173 (5)
H40.22210.28350.02560.021*
C50.4269 (3)0.3583 (3)0.06637 (9)0.0240 (7)
H5A0.48920.27180.06950.036*
H5B0.43620.40900.09500.036*
H5C0.48140.41040.04160.036*
C60.1334 (3)0.2460 (2)0.09118 (8)0.0151 (5)
H60.12360.30200.11940.018*
C70.2146 (3)0.1081 (3)0.10554 (9)0.0149 (5)
C80.2666 (4)0.0269 (3)0.06281 (9)0.0211 (6)
H8A0.3166−0.06030.07200.032*
H8B0.35590.07730.04530.032*
H8C0.16020.01210.04390.032*
C90.3702 (4)0.1130 (2)0.13960 (8)0.0175 (5)
H9A0.34180.17850.16400.021*
H9B0.47920.14490.12380.021*
C100.4070 (3)−0.0258 (3)0.16101 (9)0.0200 (6)
H10A0.4509−0.08780.13700.024*
H10B0.5029−0.01630.18410.024*
C110.2430 (3)−0.0883 (3)0.18361 (9)0.0158 (5)
H110.2062−0.02410.20820.019*
C120.2789 (3)−0.2260 (3)0.20769 (9)0.0210 (6)
C130.3411 (4)−0.3321 (3)0.17341 (10)0.0308 (7)
H13A0.2498−0.34350.14980.046*
H13B0.3600−0.41820.18910.046*
H13C0.4533−0.30270.15930.046*
C140.4248 (3)−0.2139 (3)0.24460 (9)0.0228 (6)
H14A0.4535−0.30550.25600.027*
H14B0.5344−0.17700.23040.027*
C150.3754 (4)−0.1259 (3)0.28485 (9)0.0246 (6)
H15A0.4739−0.12700.30740.030*
H15B0.3588−0.03170.27440.030*
C160.2049 (4)−0.1755 (3)0.30718 (10)0.0300 (7)
H16A0.1701−0.11250.33180.036*
H16B0.2262−0.26520.32100.036*
C170.0533 (4)−0.1856 (3)0.27254 (10)0.0284 (7)
H17A0.0218−0.09400.26180.034*
H17B−0.0534−0.22460.28760.034*
C180.1038 (3)−0.2733 (3)0.23142 (9)0.0248 (6)
H180.1264−0.36640.24330.030*
C19−0.0515 (4)−0.2839 (3)0.19738 (11)0.0302 (7)
H19A−0.0243−0.35490.17470.036*
H19B−0.1615−0.31060.21380.036*
C20−0.0845 (3)−0.1502 (3)0.17263 (10)0.0239 (7)
H20A−0.1298−0.08290.19470.029*
H20B−0.1777−0.16370.14910.029*
C210.0841 (3)−0.0953 (3)0.15005 (9)0.0166 (6)
H210.1174−0.15680.12440.020*
C220.0536 (3)0.0461 (3)0.13073 (9)0.0156 (5)
H220.03080.10580.15760.019*
C23−0.1020 (4)0.0685 (2)0.09833 (8)0.0184 (6)
H23A−0.21700.07030.11500.022*
H23B−0.1069−0.00310.07480.022*
C24−0.0613 (3)0.2077 (3)0.07660 (9)0.0174 (6)
H24A−0.14720.27630.08770.021*
H24B−0.07030.20230.04300.021*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.02565 (13)0.02078 (12)0.02645 (13)0.00045 (12)−0.00377 (13)0.00517 (11)
C10.0273 (18)0.0216 (13)0.0184 (14)0.0042 (12)0.0029 (11)0.0008 (11)
C20.0125 (13)0.0209 (13)0.0198 (14)−0.0004 (11)−0.0018 (11)0.0013 (11)
C30.0215 (13)0.0207 (12)0.0156 (12)0.0007 (12)0.0015 (14)−0.0002 (10)
C40.0148 (13)0.0203 (12)0.0169 (12)0.0011 (10)0.0006 (12)0.0010 (13)
C50.0177 (15)0.0284 (15)0.0258 (16)−0.0027 (11)0.0000 (11)0.0082 (12)
C60.0133 (11)0.0166 (13)0.0155 (11)−0.0001 (12)−0.0003 (10)−0.0027 (9)
C70.0125 (13)0.0173 (13)0.0150 (13)0.0006 (11)−0.0004 (11)−0.0007 (10)
C80.0208 (15)0.0229 (14)0.0196 (16)0.0036 (11)0.0036 (12)−0.0038 (11)
C90.0101 (12)0.0223 (13)0.0201 (13)−0.0011 (13)−0.0003 (13)0.0032 (10)
C100.0151 (15)0.0228 (13)0.0223 (14)−0.0009 (11)−0.0023 (12)0.0019 (11)
C110.0144 (13)0.0151 (13)0.0180 (13)0.0021 (10)−0.0041 (11)−0.0013 (11)
C120.0184 (13)0.0169 (12)0.0278 (14)0.0013 (12)−0.0053 (11)0.0030 (13)
C130.0326 (19)0.0209 (14)0.0389 (18)0.0089 (13)−0.0092 (15)0.0002 (13)
C140.0150 (13)0.0214 (14)0.0321 (15)0.0004 (11)−0.0032 (11)0.0099 (13)
C150.0285 (15)0.0217 (13)0.0236 (14)−0.0023 (15)−0.0098 (15)0.0064 (11)
C160.0326 (17)0.0320 (16)0.0254 (16)−0.0009 (14)−0.0012 (14)0.0102 (13)
C170.0218 (15)0.0290 (16)0.0343 (17)−0.0024 (12)0.0024 (13)0.0150 (13)
C180.0205 (13)0.0162 (11)0.0378 (15)−0.0044 (14)−0.0080 (12)0.0103 (12)
C190.0254 (15)0.0214 (14)0.0439 (18)−0.0079 (14)−0.0070 (14)0.0090 (15)
C200.0151 (15)0.0234 (14)0.0331 (16)−0.0040 (11)−0.0063 (12)0.0059 (12)
C210.0129 (14)0.0166 (12)0.0203 (13)0.0005 (10)−0.0044 (11)−0.0001 (10)
C220.0113 (12)0.0155 (13)0.0202 (14)0.0018 (10)−0.0022 (11)−0.0046 (11)
C230.0147 (14)0.0220 (13)0.0184 (13)−0.0029 (12)−0.0040 (12)0.0009 (10)
C240.0116 (12)0.0237 (14)0.0168 (13)0.0018 (10)−0.0005 (10)0.0018 (11)

Geometric parameters (Å, °)

Br1—C11.956 (3)C12—C141.542 (3)
C1—C21.511 (4)C12—C181.555 (4)
C1—H1A0.9900C13—H13A0.9800
C1—H1B0.9900C13—H13B0.9800
C2—C31.528 (3)C13—H13C0.9800
C2—H2A0.9900C14—C151.514 (4)
C2—H2B0.9900C14—H14A0.9900
C3—C41.538 (3)C14—H14B0.9900
C3—H3A0.9900C15—C161.515 (4)
C3—H3B0.9900C15—H15A0.9900
C4—C61.530 (3)C15—H15B0.9900
C4—C51.542 (3)C16—C171.526 (4)
C4—H41.0000C16—H16A0.9900
C5—H5A0.9800C16—H16B0.9900
C5—H5B0.9800C17—C181.534 (4)
C5—H5C0.9800C17—H17A0.9900
C6—C71.553 (3)C17—H17B0.9900
C6—C241.565 (3)C18—C191.536 (4)
C6—H61.0000C18—H181.0000
C7—C91.535 (4)C19—C201.530 (4)
C7—C81.539 (3)C19—H19A0.9900
C7—C221.541 (4)C19—H19B0.9900
C8—H8A0.9800C20—C211.525 (3)
C8—H8B0.9800C20—H20A0.9900
C8—H8C0.9800C20—H20B0.9900
C9—C101.537 (3)C21—C221.529 (4)
C9—H9A0.9900C21—H211.0000
C9—H9B0.9900C22—C231.519 (4)
C10—C111.526 (4)C22—H221.0000
C10—H10A0.9900C23—C241.550 (3)
C10—H10B0.9900C23—H23A0.9900
C11—C211.545 (3)C23—H23B0.9900
C11—C121.560 (4)C24—H24A0.9900
C11—H111.0000C24—H24B0.9900
C12—C131.527 (4)
C2—C1—Br1112.46 (18)C12—C13—H13A109.5
C2—C1—H1A109.1C12—C13—H13B109.5
Br1—C1—H1A109.1H13A—C13—H13B109.5
C2—C1—H1B109.1C12—C13—H13C109.5
Br1—C1—H1B109.1H13A—C13—H13C109.5
H1A—C1—H1B107.8H13B—C13—H13C109.5
C1—C2—C3110.9 (2)C15—C14—C12114.8 (2)
C1—C2—H2A109.5C15—C14—H14A108.6
C3—C2—H2A109.5C12—C14—H14A108.6
C1—C2—H2B109.5C15—C14—H14B108.6
C3—C2—H2B109.5C12—C14—H14B108.6
H2A—C2—H2B108.1H14A—C14—H14B107.5
C2—C3—C4114.1 (2)C16—C15—C14110.8 (2)
C2—C3—H3A108.7C16—C15—H15A109.5
C4—C3—H3A108.7C14—C15—H15A109.5
C2—C3—H3B108.7C16—C15—H15B109.5
C4—C3—H3B108.7C14—C15—H15B109.5
H3A—C3—H3B107.6H15A—C15—H15B108.1
C6—C4—C3110.0 (2)C15—C16—C17111.0 (2)
C6—C4—C5113.3 (2)C15—C16—H16A109.4
C3—C4—C5109.7 (2)C17—C16—H16A109.4
C6—C4—H4107.9C15—C16—H16B109.4
C3—C4—H4107.9C17—C16—H16B109.4
C5—C4—H4107.9H16A—C16—H16B108.0
C4—C5—H5A109.5C16—C17—C18112.2 (2)
C4—C5—H5B109.5C16—C17—H17A109.2
H5A—C5—H5B109.5C18—C17—H17A109.2
C4—C5—H5C109.5C16—C17—H17B109.2
H5A—C5—H5C109.5C18—C17—H17B109.2
H5B—C5—H5C109.5H17A—C17—H17B107.9
C4—C6—C7119.9 (2)C19—C18—C17111.3 (2)
C4—C6—C24112.27 (19)C19—C18—C12111.5 (2)
C7—C6—C24103.01 (19)C17—C18—C12112.9 (2)
C4—C6—H6107.0C19—C18—H18106.9
C7—C6—H6107.0C17—C18—H18106.9
C24—C6—H6107.0C12—C18—H18106.9
C9—C7—C8110.8 (2)C20—C19—C18111.8 (2)
C9—C7—C22107.0 (2)C20—C19—H19A109.3
C8—C7—C22112.3 (2)C18—C19—H19A109.3
C9—C7—C6116.4 (2)C20—C19—H19B109.3
C8—C7—C6109.7 (2)C18—C19—H19B109.3
C22—C7—C6100.12 (19)H19A—C19—H19B107.9
C7—C8—H8A109.5C19—C20—C21112.4 (2)
C7—C8—H8B109.5C19—C20—H20A109.1
H8A—C8—H8B109.5C21—C20—H20A109.1
C7—C8—H8C109.5C19—C20—H20B109.1
H8A—C8—H8C109.5C21—C20—H20B109.1
H8B—C8—H8C109.5H20A—C20—H20B107.8
C7—C9—C10111.9 (2)C22—C21—C20111.4 (2)
C7—C9—H9A109.2C22—C21—C11108.0 (2)
C10—C9—H9A109.2C20—C21—C11112.1 (2)
C7—C9—H9B109.2C22—C21—H21108.4
C10—C9—H9B109.2C20—C21—H21108.4
H9A—C9—H9B107.9C11—C21—H21108.4
C11—C10—C9113.4 (2)C23—C22—C21118.7 (2)
C11—C10—H10A108.9C23—C22—C7103.9 (2)
C9—C10—H10A108.9C21—C22—C7115.3 (2)
C11—C10—H10B108.9C23—C22—H22106.0
C9—C10—H10B108.9C21—C22—H22106.0
H10A—C10—H10B107.7C7—C22—H22106.0
C10—C11—C21111.1 (2)C22—C23—C24103.7 (2)
C10—C11—C12114.4 (2)C22—C23—H23A111.0
C21—C11—C12112.4 (2)C24—C23—H23A111.0
C10—C11—H11106.1C22—C23—H23B111.0
C21—C11—H11106.1C24—C23—H23B111.0
C12—C11—H11106.1H23A—C23—H23B109.0
C13—C12—C14107.5 (2)C23—C24—C6106.6 (2)
C13—C12—C18110.1 (2)C23—C24—H24A110.4
C14—C12—C18107.8 (2)C6—C24—H24A110.4
C13—C12—C11110.9 (2)C23—C24—H24B110.4
C14—C12—C11111.8 (2)C6—C24—H24B110.4
C18—C12—C11108.8 (2)H24A—C24—H24B108.6
Br1—C1—C2—C3−172.81 (18)C16—C17—C18—C19179.2 (2)
C1—C2—C3—C4179.6 (2)C16—C17—C18—C12−54.6 (3)
C2—C3—C4—C6−165.3 (2)C13—C12—C18—C19−64.9 (3)
C2—C3—C4—C569.4 (3)C14—C12—C18—C19178.1 (2)
C3—C4—C6—C7−175.8 (2)C11—C12—C18—C1956.8 (3)
C5—C4—C6—C7−52.6 (3)C13—C12—C18—C17168.9 (2)
C3—C4—C6—C2463.2 (3)C14—C12—C18—C1752.0 (3)
C5—C4—C6—C24−173.6 (2)C11—C12—C18—C17−69.4 (3)
C4—C6—C7—C979.4 (3)C17—C18—C19—C2070.3 (3)
C24—C6—C7—C9−155.1 (2)C12—C18—C19—C20−56.7 (3)
C4—C6—C7—C8−47.5 (3)C18—C19—C20—C2153.6 (3)
C24—C6—C7—C878.0 (2)C19—C20—C21—C22−172.9 (2)
C4—C6—C7—C22−165.7 (2)C19—C20—C21—C11−51.7 (3)
C24—C6—C7—C22−40.2 (2)C10—C11—C21—C22−53.7 (3)
C8—C7—C9—C10−68.8 (3)C12—C11—C21—C22176.6 (2)
C22—C7—C9—C1053.9 (3)C10—C11—C21—C20−176.8 (2)
C6—C7—C9—C10164.8 (2)C12—C11—C21—C2053.5 (3)
C7—C9—C10—C11−55.0 (3)C20—C21—C22—C23−53.6 (3)
C9—C10—C11—C2154.2 (3)C11—C21—C22—C23−177.1 (2)
C9—C10—C11—C12−177.2 (2)C20—C21—C22—C7−177.7 (2)
C10—C11—C12—C13−62.0 (3)C11—C21—C22—C758.8 (3)
C21—C11—C12—C1365.9 (3)C9—C7—C22—C23169.8 (2)
C10—C11—C12—C1457.9 (3)C8—C7—C22—C23−68.4 (3)
C21—C11—C12—C14−174.1 (2)C6—C7—C22—C2347.9 (2)
C10—C11—C12—C18176.8 (2)C9—C7—C22—C21−58.6 (3)
C21—C11—C12—C18−55.3 (3)C8—C7—C22—C2163.2 (3)
C13—C12—C14—C15−172.6 (2)C6—C7—C22—C21179.6 (2)
C18—C12—C14—C15−53.9 (3)C21—C22—C23—C24−165.6 (2)
C11—C12—C14—C1565.5 (3)C7—C22—C23—C24−36.0 (2)
C12—C14—C15—C1656.6 (3)C22—C23—C24—C610.0 (3)
C14—C15—C16—C17−54.7 (3)C4—C6—C24—C23149.5 (2)
C15—C16—C17—C1854.7 (3)C7—C6—C24—C2319.2 (2)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2433).

References

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