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Acta Cryst. (2010). E66, o2092    [ doi:10.1107/S1600536810028412 ]

10,13-Dimethyl-16-oxo-4,5,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl acetate

R. Shi, C.-S. Zhang, R. Huang and K. Wei

Abstract top

In the title compound, C21H30O3, the five-membered ring adopts an envelope conformation, the cyclohexene ring displays a half-chair conformation and the two cyclohexane rings have normal chair conformations. In the crystal structure, weak intermolecular C-H...O hydrogen bonding links the molecules into supramolecular chains running along [100].

Comment top

Rocuronium is a nondepolarizing neuromuscular blocking agent, which produces neuromuscular blockade by competing with acetylcholine for cholinergic receptors at the motor end plate (Tuba et al., 2002; Auer, 2007). The title compound was obtained as an intermediate during our ongoing investigation of the synthese of rocuronium bromide. In this paper, we report the crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. In the molecular structure, the cyclohexene ring displays a half-chair conformtion, the five ring adopts an envelope conformation, and two cyclohexane rings have the normal chair conformation. In the crystal structure weak intermolecular C—H···O hydrogen bonding links the molecules to form the supra-molecular chain running along the [1 0 0] direction (Table 1).

Related literature top

Rocuronium is a non-depolarizing neuromuscular blocking agent. The title compound was obtained as an intermediate during our ongoing investigation of the synthesis of rocuronium bromide; for further information on rocuronium bromide, see: Tuba et al. (2002); Auer (2007). For the synthesis, see: Tuba (1980); Newaz & Tcholakian (1984).

Experimental top

The title compound was synthesized according to the procedure reported by Tuba et al. (1980) and by Newaz & Tcholakian (1984). Single crystals were obtained from a mixture of ethyl acetate and petroleum ether by slow evaporation at room temperature.

Refinement top

All H atoms were placed in calculated positions, with C—H = 0.93–0.98 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C). Friedel paris were merged as no significant anomalous scattering.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atom labelling scheme and 30% probability displacement ellipsoids.
10,13-Dimethyl-16-oxo-4,5,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro- 1H-cyclopenta[a]phenanthren-17-yl acetate top
Crystal data top
C21H30O3F(000) = 360
Mr = 330.45Dx = 1.150 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 864 reflections
a = 7.383 (5) Åθ = 5.7–25.7°
b = 13.200 (9) ŵ = 0.08 mm−1
c = 9.843 (7) ÅT = 293 K
β = 95.687 (10)°Block, colorless
V = 954.5 (11) Å30.45 × 0.40 × 0.32 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer		864 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.102
graphiteθmax = 25.2°, θmin = 2.1°
φ and ω scansh = −8→8
5527 measured reflectionsk = −9→15
1794 independent reflectionsl = −11→11
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.136 w = 1/[σ2(Fo2) + (0.0539P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.86(Δ/σ)max < 0.001
1794 reflectionsΔρmax = 0.13 e Å−3
221 parametersΔρmin = −0.11 e Å−3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.018 (3)
Crystal data top
C21H30O3V = 954.5 (11) Å3
Mr = 330.45Z = 2
Monoclinic, P21Mo Kα radiation
a = 7.383 (5) ŵ = 0.08 mm−1
b = 13.200 (9) ÅT = 293 K
c = 9.843 (7) Å0.45 × 0.40 × 0.32 mm
β = 95.687 (10)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		864 reflections with I > 2σ(I)
5527 measured reflectionsRint = 0.102
1794 independent reflectionsθmax = 25.2°
Refinement top
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.136Δρmax = 0.13 e Å−3
S = 0.86Δρmin = −0.11 e Å−3
1794 reflectionsAbsolute structure: ?
221 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Special details top

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2353 (9)0.8413 (7)0.3971 (7)0.089 (2)
H1A0.10470.83160.38090.107*
H1B0.27560.81000.48410.107*
C20.2742 (13)0.9525 (7)0.4068 (8)0.104 (3)
H20.19750.99380.45190.125*
C30.4149 (14)0.9942 (7)0.3531 (9)0.109 (3)
H30.43061.06400.35970.130*
C40.5469 (11)0.9345 (7)0.2835 (8)0.100 (2)
H4A0.66900.95450.31870.120*
H4B0.53180.95060.18680.120*
C50.5277 (9)0.8189 (6)0.3009 (7)0.084 (2)
H50.57530.80280.39490.100*
C60.6463 (9)0.7619 (6)0.2068 (8)0.090 (2)
H6A0.60530.77720.11230.108*
H6B0.77160.78420.22450.108*
C70.6356 (8)0.6477 (6)0.2303 (7)0.087 (2)
H7A0.70520.61290.16600.104*
H7B0.68960.63190.32170.104*
C80.4396 (8)0.6097 (5)0.2132 (6)0.0669 (18)
H80.38950.61920.11810.080*
C90.3222 (8)0.6712 (6)0.3088 (6)0.0703 (19)
H90.37700.65990.40230.084*
C100.3266 (8)0.7864 (5)0.2843 (6)0.0674 (18)
C110.1274 (8)0.6266 (6)0.3010 (7)0.083 (2)
H11A0.06030.66100.36730.100*
H11B0.06600.64000.21110.100*
C120.1231 (9)0.5120 (7)0.3282 (7)0.089 (2)
H12A0.17190.49870.42170.107*
H12B−0.00190.48840.31700.107*
C130.2347 (8)0.4539 (5)0.2304 (6)0.0716 (19)
C140.4277 (8)0.4979 (5)0.2504 (6)0.067 (2)
H140.46740.49280.34810.081*
C150.5425 (9)0.4225 (6)0.1788 (7)0.091 (2)
H15A0.54040.43780.08230.110*
H15B0.66770.42230.21950.110*
C160.4499 (12)0.3221 (8)0.2014 (8)0.100 (3)
C170.2753 (9)0.3439 (6)0.2690 (7)0.0768 (19)
H170.30090.33850.36830.092*
C180.0718 (10)0.2130 (6)0.3117 (10)0.084 (2)
C19−0.0681 (10)0.1408 (6)0.2474 (8)0.116 (3)
H19A−0.08500.08640.30970.174*
H19B−0.02760.11380.16500.174*
H19C−0.18130.17580.22620.174*
C200.2325 (8)0.8158 (5)0.1428 (6)0.083 (2)
H20A0.10550.79900.13840.125*
H20B0.28760.77940.07320.125*
H20C0.24570.88730.12880.125*
C210.1481 (8)0.4600 (5)0.0849 (6)0.083 (2)
H21A0.21560.41870.02730.125*
H21B0.14890.52900.05420.125*
H21C0.02490.43610.08060.125*
O10.4948 (9)0.2388 (5)0.1678 (7)0.129 (2)
O20.1340 (7)0.2744 (4)0.2230 (5)0.0994 (16)
O30.1307 (8)0.2124 (5)0.4295 (6)0.127 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.089 (5)0.107 (7)0.075 (5)0.001 (5)0.020 (4)−0.015 (5)
C20.122 (7)0.091 (7)0.098 (6)0.004 (5)0.007 (5)−0.003 (5)
C30.123 (7)0.094 (7)0.104 (7)−0.012 (7)−0.012 (6)−0.010 (6)
C40.092 (6)0.108 (7)0.099 (6)−0.036 (5)0.000 (5)0.003 (5)
C50.067 (5)0.100 (7)0.083 (5)−0.012 (4)0.000 (4)0.001 (4)
C60.057 (4)0.096 (6)0.119 (6)−0.014 (4)0.016 (4)0.008 (5)
C70.051 (4)0.103 (6)0.109 (6)−0.010 (4)0.016 (4)0.003 (5)
C80.052 (4)0.082 (6)0.064 (4)−0.001 (4)−0.005 (3)0.015 (4)
C90.041 (4)0.102 (6)0.069 (5)−0.014 (4)0.015 (3)−0.002 (4)
C100.057 (4)0.083 (6)0.062 (4)−0.005 (4)0.001 (4)−0.001 (4)
C110.047 (4)0.114 (7)0.091 (6)−0.010 (4)0.020 (4)−0.005 (5)
C120.064 (5)0.125 (7)0.079 (5)−0.025 (4)0.016 (4)0.011 (5)
C130.057 (4)0.104 (6)0.054 (4)−0.014 (4)0.005 (3)−0.002 (4)
C140.056 (4)0.090 (6)0.058 (4)−0.001 (4)0.015 (3)−0.005 (4)
C150.067 (5)0.102 (6)0.104 (6)−0.006 (5)0.005 (4)0.009 (5)
C160.088 (6)0.109 (8)0.099 (6)0.004 (6)−0.010 (5)0.012 (7)
C170.068 (5)0.083 (6)0.077 (5)−0.018 (5)−0.003 (4)0.014 (4)
C180.076 (5)0.083 (6)0.094 (6)−0.002 (5)0.014 (5)−0.020 (6)
C190.088 (6)0.096 (6)0.160 (8)−0.033 (5)−0.011 (5)0.000 (5)
C200.076 (4)0.095 (6)0.077 (5)0.000 (4)−0.003 (4)0.006 (4)
C210.075 (4)0.104 (6)0.069 (5)−0.007 (4)0.001 (4)0.002 (4)
O10.124 (5)0.096 (5)0.168 (6)0.011 (4)0.022 (4)0.013 (4)
O20.107 (4)0.100 (4)0.087 (4)−0.037 (3)−0.008 (3)0.020 (3)
O30.141 (5)0.142 (5)0.100 (4)−0.057 (4)0.027 (4)0.001 (4)
Geometric parameters (Å, °) top
C1—C21.497 (11)C11—H11B0.9700
C1—C101.536 (8)C12—C131.534 (8)
C1—H1A0.9700C12—H12A0.9700
C1—H1B0.9700C12—H12B0.9700
C2—C31.331 (10)C13—C211.512 (8)
C2—H20.9300C13—C171.522 (9)
C3—C41.473 (10)C13—C141.534 (8)
C3—H30.9300C14—C151.524 (9)
C4—C51.544 (10)C14—H140.9800
C4—H4A0.9700C15—C161.517 (11)
C4—H4B0.9700C15—H15A0.9700
C5—C61.533 (8)C15—H15B0.9700
C5—C101.538 (8)C16—O11.204 (9)
C5—H50.9800C16—C171.536 (10)
C6—C71.528 (9)C17—O21.429 (7)
C6—H6A0.9700C17—H170.9800
C6—H6B0.9700C18—O31.197 (8)
C7—C81.525 (8)C18—O21.306 (9)
C7—H7A0.9700C18—C191.500 (9)
C7—H7B0.9700C19—H19A0.9600
C8—C141.525 (8)C19—H19B0.9600
C8—C91.568 (8)C19—H19C0.9600
C8—H80.9800C20—H20A0.9600
C9—C101.541 (8)C20—H20B0.9600
C9—C111.549 (7)C20—H20C0.9600
C9—H90.9800C21—H21A0.9600
C10—C201.543 (8)C21—H21B0.9600
C11—C121.536 (9)C21—H21C0.9600
C11—H11A0.9700
C2—C1—C10114.4 (7)C9—C11—H11B108.8
C2—C1—H1A108.7H11A—C11—H11B107.7
C10—C1—H1A108.7C13—C12—C11111.2 (5)
C2—C1—H1B108.7C13—C12—H12A109.4
C10—C1—H1B108.7C11—C12—H12A109.4
H1A—C1—H1B107.6C13—C12—H12B109.4
C3—C2—C1122.2 (8)C11—C12—H12B109.4
C3—C2—H2118.9H12A—C12—H12B108.0
C1—C2—H2118.9C21—C13—C17110.0 (5)
C2—C3—C4122.8 (8)C21—C13—C12111.4 (5)
C2—C3—H3118.6C17—C13—C12115.2 (6)
C4—C3—H3118.6C21—C13—C14113.6 (5)
C3—C4—C5113.9 (7)C17—C13—C1499.9 (5)
C3—C4—H4A108.8C12—C13—C14106.3 (5)
C5—C4—H4A108.8C15—C14—C8118.2 (5)
C3—C4—H4B108.8C15—C14—C13104.2 (5)
C5—C4—H4B108.8C8—C14—C13114.3 (6)
H4A—C4—H4B107.7C15—C14—H14106.4
C6—C5—C10113.7 (6)C8—C14—H14106.4
C6—C5—C4110.7 (6)C13—C14—H14106.4
C10—C5—C4111.2 (6)C16—C15—C14102.9 (6)
C6—C5—H5106.9C16—C15—H15A111.2
C10—C5—H5106.9C14—C15—H15A111.2
C4—C5—H5106.9C16—C15—H15B111.2
C7—C6—C5110.6 (6)C14—C15—H15B111.2
C7—C6—H6A109.5H15A—C15—H15B109.1
C5—C6—H6A109.5O1—C16—C15128.1 (8)
C7—C6—H6B109.5O1—C16—C17123.8 (9)
C5—C6—H6B109.5C15—C16—C17108.1 (8)
H6A—C6—H6B108.1O2—C17—C13114.5 (5)
C8—C7—C6111.8 (6)O2—C17—C16111.1 (6)
C8—C7—H7A109.3C13—C17—C16102.9 (6)
C6—C7—H7A109.3O2—C17—H17109.4
C8—C7—H7B109.3C13—C17—H17109.4
C6—C7—H7B109.3C16—C17—H17109.4
H7A—C7—H7B107.9O3—C18—O2122.2 (8)
C14—C8—C7111.6 (5)O3—C18—C19125.0 (9)
C14—C8—C9108.0 (5)O2—C18—C19112.7 (8)
C7—C8—C9109.8 (5)C18—C19—H19A109.5
C14—C8—H8109.1C18—C19—H19B109.5
C7—C8—H8109.1H19A—C19—H19B109.5
C9—C8—H8109.1C18—C19—H19C109.5
C10—C9—C11113.7 (6)H19A—C19—H19C109.5
C10—C9—C8113.3 (5)H19B—C19—H19C109.5
C11—C9—C8109.9 (5)C10—C20—H20A109.5
C10—C9—H9106.5C10—C20—H20B109.5
C11—C9—H9106.5H20A—C20—H20B109.5
C8—C9—H9106.5C10—C20—H20C109.5
C1—C10—C5106.3 (6)H20A—C20—H20C109.5
C1—C10—C9109.5 (6)H20B—C20—H20C109.5
C5—C10—C9107.1 (5)C13—C21—H21A109.5
C1—C10—C20110.1 (5)C13—C21—H21B109.5
C5—C10—C20111.7 (5)H21A—C21—H21B109.5
C9—C10—C20112.0 (5)C13—C21—H21C109.5
C12—C11—C9113.6 (6)H21A—C21—H21C109.5
C12—C11—H11A108.8H21B—C21—H21C109.5
C9—C11—H11A108.8C18—O2—C17118.7 (6)
C12—C11—H11B108.8
C10—C1—C2—C3−19.1 (10)C11—C12—C13—C21−67.3 (7)
C1—C2—C3—C4−1.9 (13)C11—C12—C13—C17166.6 (5)
C2—C3—C4—C5−10.3 (11)C11—C12—C13—C1457.0 (7)
C3—C4—C5—C6170.4 (6)C7—C8—C14—C15−54.7 (8)
C3—C4—C5—C1043.0 (8)C9—C8—C14—C15−175.5 (5)
C10—C5—C6—C7−57.3 (8)C7—C8—C14—C13−177.9 (5)
C4—C5—C6—C7176.7 (6)C9—C8—C14—C1361.3 (6)
C5—C6—C7—C855.4 (8)C21—C13—C14—C15−70.3 (7)
C6—C7—C8—C14−174.4 (6)C17—C13—C14—C1546.7 (6)
C6—C7—C8—C9−54.7 (7)C12—C13—C14—C15166.8 (5)
C14—C8—C9—C10178.5 (5)C21—C13—C14—C860.2 (7)
C7—C8—C9—C1056.5 (7)C17—C13—C14—C8177.3 (5)
C14—C8—C9—C11−53.2 (7)C12—C13—C14—C8−62.7 (7)
C7—C8—C9—C11−175.1 (6)C8—C14—C15—C16−161.0 (5)
C2—C1—C10—C549.1 (8)C13—C14—C15—C16−32.9 (7)
C2—C1—C10—C9164.4 (6)C14—C15—C16—O1−177.1 (9)
C2—C1—C10—C20−72.0 (7)C14—C15—C16—C176.5 (7)
C6—C5—C10—C1173.3 (7)C21—C13—C17—O2−42.2 (7)
C4—C5—C10—C1−60.9 (7)C12—C13—C17—O284.6 (6)
C6—C5—C10—C956.3 (7)C14—C13—C17—O2−162.0 (5)
C4—C5—C10—C9−177.9 (5)C21—C13—C17—C1678.5 (6)
C6—C5—C10—C20−66.6 (8)C12—C13—C17—C16−154.6 (6)
C4—C5—C10—C2059.2 (8)C14—C13—C17—C16−41.3 (6)
C11—C9—C10—C163.0 (6)O1—C16—C17—O2−31.4 (11)
C8—C9—C10—C1−170.6 (5)C15—C16—C17—O2145.2 (6)
C11—C9—C10—C5177.9 (5)O1—C16—C17—C13−154.4 (8)
C8—C9—C10—C5−55.7 (6)C15—C16—C17—C1322.2 (7)
C11—C9—C10—C20−59.4 (7)O3—C18—O2—C17−0.9 (11)
C8—C9—C10—C2067.0 (6)C19—C18—O2—C17−176.8 (6)
C10—C9—C11—C12−178.9 (6)C13—C17—O2—C18−127.4 (6)
C8—C9—C11—C1253.0 (7)C16—C17—O2—C18116.5 (7)
C9—C11—C12—C13−56.0 (7)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C19—H19C···O1i0.962.553.496 (11)170
Symmetry codes: (i) x−1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C19—H19C···O1i0.962.553.496 (11)170
Symmetry codes: (i) x−1, y, z.
Acknowledgements top

The authors gratefully acknowledge computing time provided by the X-ray Diffraction Analysis Centre of the Key Laboratory of Medicinal Chemistry for Natural Resources (Ministry of Education), Yunnan University, China.

references
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