3β-Acet­oxy-5-hydr­oxy-15β,16β-methyl­ene-5β-androst-6-en-17-one

Zhou, W.; Zhong, G.-X.; Hu, W.-X.; Xia, C.-N.

doi:10.1107/S1600536807056000

3β-Acetoxy-5-hydroxy-15β,16β-methylene-5β-androst-6-en-17-one

W. Zhou, G.-X. Zhong, W.-X. Hu and C.-N. Xia

In the crystal structure of the title compound, C₂₂H₃₀O₄, rings A and C have slightly distorted chair conformations, ring B shows an approximate symmetric half-chair conformation and ring D is in an envelope conformation. The molecules are connected by weak intermolecular C—H

O hydrogen bonding.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056000/nc2066sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056000/nc2066Isup2.hkl Contains datablock I

CCDC reference: 672899

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R factor = 0.059
wR factor = 0.150
Data-to-parameter ratio = 10.2

checkCIF/PLATON results

No syntax errors found



Alert level C
STRVA01_ALERT_4_C           Flack parameter is too small
           From the CIF: _refine_ls_abs_structure_Flack  -10.000
           From the CIF: _refine_ls_abs_structure_Flack_su   10.000
PLAT032_ALERT_4_C Std. Uncertainty in Flack Parameter too High ...      10.00
PLAT033_ALERT_2_C Flack Parameter Value Deviates 2 * su from zero.     -10.00
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.54 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.16 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C21

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.00
           From the CIF: _reflns_number_total               2437
           Count of symmetry unique reflns         2444
           Completeness (_total/calc)             99.71%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C5     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C8     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C9     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C10    = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C13    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C14    = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C15    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C16    = .          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
  12 ALERT level G = General alerts; check

  11 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Drospirenone is a new contraceptive drug with the antimineralocorticoid and antiandrogenic properties (Muhn et al., 1995). In our attempts to synthesize this drug, the title compound, (I), was obtained as an intermediate by the reductive dechlorination of, 3β-acetoxy-7α-chloro-5,6β-epoxy-15β,16β-methylene-5β-androstan-17-one, (II). Here we report the crystal structure of (I).

In the cyclopropyl ring C15/C16/C20, the bond lengths C16—C20 and C15—C20 are different (1.524 (4) versus 1.484 (3) Å), which is also found in 3β-acetoxy-7α-chloro-5,6β-epoxy-15β,16β-methylene-5β-androstan-17-one (1.511 (5) and 1.473 (4) Å) reported previously (Zhou et al., 2007). The difference in these bond lengths might be caused by a hyperconjugation interacton between the C=O π-bonding and C16—C20 σ-bonding orbitals. However, in the analogous structure of 3 b-Acetoxy-17,17-ethylenedioxy-15b,16b-methylene-5-androsten-7 b-ol these bond lenghts are almost equal (1.499 (6) and 1.493 (6) Å) (Zhou et al., 2006).

In the steroid skeleton, the ring A and ring C show slightly distorted chair conformations, ring B shows a closely symmetric half-chair conformation and ring D is in an an envelope conformation. In ring B, atom C9 and atom C10 deviate by -0.402 (4)Å and 0.410 (4)Å from the mean plane calculated through the ring C5—C8, respectively. In ring D, C13 deviates by 0.513 (4)Å from the mean plane of C14—C17, which makes a dihedral angle of 64.6 (2)° with the cyclopropyl ring C15/C16/C20. In the structure an intramolecular O—H···O hydrogen bond is found (Table 1). In addition, two weak intermolecular C—H···O hydrogen bonds are also observed (Table 1.).

Related literature top

For related literature, see: Muhn et al. (1995) and Zhou et al. (2006, 2007); Bittler et al. (1984).

Experimental top

The title compound was synthesized according to literature methods (Bittler et al., 1984). Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of the solvent from a solution of the title compound in isopropyl ether.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Version 1.05; Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

Fig. 1. Crystal structure of (I) with labelling and displacement ellipsoids drawn at the 30% probability level.

3β-Acetoxy-5-hydroxy-15β,16β-methylene-5β-androst-6-en-17-one top

Crystal data top

C₂₂H₃₀O₄	F(000) = 776
M_r = 358.46	D_x = 1.221 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 833 reflections
a = 7.160 (4) Å	θ = 2.8–26.8°
b = 14.541 (8) Å	µ = 0.08 mm⁻¹
c = 18.733 (10) Å	T = 293 K
V = 1950.4 (18) Å³	Block, colorless
Z = 4	0.40 × 0.35 × 0.25 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2437 independent reflections
Radiation source: fine-focus sealed tube	2036 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
phi and ω scans	θ_max = 27.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −9→6
T_min = 0.957, T_max = 0.971	k = −18→13
9446 measured reflections	l = −23→23

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.059	H-atom parameters constrained
wR(F²) = 0.150	w = 1/[σ²(F_o²) + (0.0893P)²] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max < 0.001
2437 reflections	Δρ_max = 0.37 e Å⁻³
239 parameters	Δρ_min = −0.26 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.032 (4)

Crystal data top

C₂₂H₃₀O₄	V = 1950.4 (18) Å³
M_r = 358.46	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.160 (4) Å	µ = 0.08 mm⁻¹
b = 14.541 (8) Å	T = 293 K
c = 18.733 (10) Å	0.40 × 0.35 × 0.25 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2437 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	2036 reflections with I > 2σ(I)
T_min = 0.957, T_max = 0.971	R_int = 0.059
9446 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 1.17	Δρ_max = 0.37 e Å⁻³
2437 reflections	Δρ_min = −0.26 e Å⁻³
239 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
O1	0.3040 (4)	0.30323 (16)	0.11757 (11)	0.0630 (7)
O2	0.2403 (7)	0.1667 (2)	0.07470 (17)	0.1242 (17)
O3	0.3461 (4)	0.48147 (15)	0.18108 (10)	0.0544 (6)
H3	0.3806	0.4496	0.1475	0.082*
O4	0.7636 (5)	0.29845 (19)	0.60324 (13)	0.0794 (8)
C1	0.6368 (5)	0.3314 (2)	0.20925 (15)	0.0481 (7)
H1A	0.6389	0.3573	0.1615	0.058*
H1B	0.7636	0.3138	0.2213	0.058*
C2	0.5145 (5)	0.2454 (2)	0.20878 (16)	0.0548 (8)
H2A	0.5619	0.2023	0.1736	0.066*
H2B	0.5204	0.2159	0.2552	0.066*
C3	0.3140 (5)	0.2686 (2)	0.19154 (16)	0.0531 (8)
H3A	0.2365	0.2134	0.1962	0.064*
C4	0.2399 (4)	0.3433 (2)	0.23997 (15)	0.0473 (7)
H4A	0.2227	0.3175	0.2873	0.057*
H4B	0.1180	0.3618	0.2226	0.057*
C5	0.3625 (4)	0.42965 (19)	0.24669 (13)	0.0385 (6)
C6	0.2822 (4)	0.4891 (2)	0.30472 (15)	0.0438 (6)
H6	0.1752	0.5226	0.2940	0.053*
C7	0.3512 (4)	0.49757 (18)	0.36930 (14)	0.0396 (6)
H7	0.2857	0.5326	0.4025	0.048*
C8	0.5309 (3)	0.45324 (17)	0.39208 (12)	0.0316 (5)
H8	0.6304	0.4995	0.3902	0.038*
C9	0.5828 (4)	0.37321 (18)	0.34103 (13)	0.0334 (5)
H9	0.4852	0.3266	0.3469	0.040*
C10	0.5714 (4)	0.40595 (18)	0.26191 (13)	0.0358 (6)
C11	0.7666 (4)	0.3270 (2)	0.36250 (15)	0.0477 (7)
H11A	0.8686	0.3696	0.3544	0.057*
H11B	0.7869	0.2738	0.3322	0.057*
C12	0.7699 (5)	0.2960 (2)	0.44137 (15)	0.0495 (8)
H12A	0.6788	0.2475	0.4487	0.059*
H12B	0.8923	0.2719	0.4533	0.059*
C13	0.7241 (4)	0.37802 (19)	0.48968 (13)	0.0393 (6)
C14	0.5262 (4)	0.41171 (17)	0.46729 (13)	0.0334 (6)
H14	0.4524	0.3553	0.4623	0.040*
C15	0.4424 (4)	0.4606 (2)	0.53111 (13)	0.0420 (6)
H15	0.3062	0.4661	0.5337	0.050*
C16	0.5460 (4)	0.4216 (2)	0.59609 (14)	0.0479 (7)
H16	0.4739	0.4039	0.6384	0.057*
C17	0.6908 (5)	0.3584 (2)	0.56908 (15)	0.0482 (7)
C18	0.8868 (4)	0.4478 (3)	0.48569 (17)	0.0540 (8)
H18A	0.9279	0.4626	0.5331	0.081*
H18B	0.8449	0.5028	0.4622	0.081*
H18C	0.9884	0.4214	0.4593	0.081*
C19	0.6941 (4)	0.4917 (2)	0.25053 (15)	0.0486 (7)
H19A	0.6896	0.5095	0.2012	0.073*
H19B	0.8206	0.4778	0.2636	0.073*
H19C	0.6485	0.5411	0.2797	0.073*
C20	0.5571 (5)	0.5230 (2)	0.57580 (15)	0.0520 (8)
H20A	0.4920	0.5667	0.6059	0.062*
H20B	0.6737	0.5453	0.5559	0.062*
C21	0.2665 (6)	0.2466 (2)	0.06563 (18)	0.0650 (10)
C22	0.2613 (7)	0.2936 (3)	−0.00473 (18)	0.0801 (13)
H22A	0.2474	0.2487	−0.0419	0.120*
H22B	0.3755	0.3270	−0.0117	0.120*
H22C	0.1578	0.3355	−0.0060	0.120*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0952 (18)	0.0565 (12)	0.0374 (10)	−0.0129 (14)	−0.0124 (12)	−0.0032 (9)
O2	0.236 (5)	0.0564 (17)	0.0799 (19)	−0.005 (2)	−0.055 (3)	−0.0110 (15)
O3	0.0732 (15)	0.0544 (12)	0.0357 (10)	0.0020 (11)	−0.0109 (10)	0.0095 (9)
O4	0.104 (2)	0.0818 (17)	0.0527 (14)	0.0325 (16)	−0.0088 (14)	0.0228 (13)
C1	0.0591 (18)	0.0529 (17)	0.0323 (13)	0.0073 (15)	0.0072 (13)	−0.0005 (12)
C2	0.085 (2)	0.0410 (16)	0.0381 (14)	0.0076 (17)	0.0014 (15)	−0.0057 (12)
C3	0.075 (2)	0.0442 (15)	0.0402 (15)	−0.0139 (16)	−0.0062 (15)	−0.0001 (12)
C4	0.0478 (17)	0.0592 (18)	0.0350 (13)	−0.0089 (14)	−0.0037 (12)	0.0012 (12)
C5	0.0430 (15)	0.0430 (14)	0.0295 (12)	0.0001 (12)	−0.0034 (11)	0.0060 (10)
C6	0.0413 (14)	0.0465 (15)	0.0437 (14)	0.0107 (13)	−0.0089 (12)	0.0013 (12)
C7	0.0418 (14)	0.0388 (14)	0.0382 (13)	0.0113 (12)	0.0003 (12)	−0.0013 (11)
C8	0.0330 (12)	0.0321 (12)	0.0297 (11)	−0.0001 (10)	−0.0005 (10)	0.0000 (10)
C9	0.0365 (13)	0.0337 (12)	0.0299 (11)	0.0000 (11)	0.0019 (10)	0.0019 (10)
C10	0.0414 (14)	0.0370 (13)	0.0291 (12)	−0.0007 (11)	0.0036 (11)	0.0025 (10)
C11	0.0537 (17)	0.0495 (16)	0.0399 (14)	0.0154 (14)	0.0015 (14)	−0.0004 (12)
C12	0.0561 (19)	0.0487 (16)	0.0437 (15)	0.0211 (15)	−0.0045 (14)	0.0039 (13)
C13	0.0400 (13)	0.0415 (14)	0.0363 (13)	0.0065 (12)	−0.0066 (11)	0.0032 (11)
C14	0.0329 (12)	0.0369 (13)	0.0302 (12)	−0.0014 (10)	−0.0020 (10)	−0.0004 (10)
C15	0.0395 (14)	0.0560 (16)	0.0305 (12)	0.0006 (13)	−0.0016 (12)	−0.0008 (12)
C16	0.0522 (17)	0.0620 (18)	0.0294 (13)	−0.0018 (15)	−0.0038 (12)	0.0013 (12)
C17	0.0529 (16)	0.0534 (17)	0.0383 (14)	−0.0017 (15)	−0.0109 (13)	0.0060 (13)
C18	0.0366 (15)	0.072 (2)	0.0537 (17)	−0.0035 (14)	−0.0084 (13)	0.0048 (16)
C19	0.0515 (17)	0.0524 (16)	0.0418 (14)	−0.0116 (14)	0.0065 (13)	0.0079 (13)
C20	0.0631 (18)	0.0525 (17)	0.0403 (15)	0.0057 (16)	−0.0057 (14)	−0.0125 (13)
C21	0.090 (3)	0.0481 (18)	0.0573 (19)	0.0094 (19)	−0.0220 (19)	−0.0121 (15)
C22	0.114 (3)	0.083 (3)	0.0432 (17)	0.017 (3)	−0.018 (2)	−0.0103 (18)

Geometric parameters (Å, º) top

O1—C21	1.303 (4)	C10—C19	1.540 (4)
O1—C3	1.476 (4)	C11—C12	1.545 (4)
O2—C21	1.188 (4)	C11—H11A	0.9700
O3—C5	1.446 (3)	C11—H11B	0.9700
O3—H3	0.8200	C12—C13	1.533 (4)
O4—C17	1.200 (4)	C12—H12A	0.9700
C1—C2	1.527 (5)	C12—H12B	0.9700
C1—C10	1.539 (4)	C13—C17	1.533 (4)
C1—H1A	0.9700	C13—C18	1.546 (4)
C1—H1B	0.9700	C13—C14	1.557 (4)
C2—C3	1.510 (5)	C14—C15	1.515 (4)
C2—H2A	0.9700	C14—H14	0.9800
C2—H2B	0.9700	C15—C20	1.483 (4)
C3—C4	1.511 (4)	C15—C16	1.534 (4)
C3—H3A	0.9800	C15—H15	0.9800
C4—C5	1.537 (4)	C16—C17	1.475 (5)
C4—H4A	0.9700	C16—C20	1.524 (4)
C4—H4B	0.9700	C16—H16	0.9800
C5—C6	1.503 (4)	C18—H18A	0.9599
C5—C10	1.561 (4)	C18—H18B	0.9599
C6—C7	1.313 (4)	C18—H18C	0.9599
C6—H6	0.9300	C19—H19A	0.9599
C7—C8	1.501 (3)	C19—H19B	0.9599
C7—H7	0.9300	C19—H19C	0.9599
C8—C14	1.533 (3)	C20—H20A	0.9700
C8—C9	1.551 (3)	C20—H20B	0.9700
C8—H8	0.9800	C21—C22	1.485 (5)
C9—C11	1.532 (4)	C22—H22A	0.9599
C9—C10	1.559 (3)	C22—H22B	0.9599
C9—H9	0.9800	C22—H22C	0.9599

C21—O1—C3	119.7 (3)	H11A—C11—H11B	107.8
C5—O3—H3	109.5	C13—C12—C11	109.5 (2)
C2—C1—C10	114.0 (2)	C13—C12—H12A	109.8
C2—C1—H1A	108.8	C11—C12—H12A	109.8
C10—C1—H1A	108.8	C13—C12—H12B	109.8
C2—C1—H1B	108.8	C11—C12—H12B	109.8
C10—C1—H1B	108.8	H12A—C12—H12B	108.2
H1A—C1—H1B	107.7	C12—C13—C17	117.4 (2)
C3—C2—C1	111.3 (3)	C12—C13—C18	108.7 (3)
C3—C2—H2A	109.4	C17—C13—C18	106.6 (2)
C1—C2—H2A	109.4	C12—C13—C14	106.3 (2)
C3—C2—H2B	109.4	C17—C13—C14	100.3 (2)
C1—C2—H2B	109.4	C18—C13—C14	117.8 (2)
H2A—C2—H2B	108.0	C15—C14—C8	123.3 (2)
O1—C3—C2	108.9 (3)	C15—C14—C13	107.2 (2)
O1—C3—C4	107.5 (3)	C8—C14—C13	110.6 (2)
C2—C3—C4	111.5 (3)	C15—C14—H14	104.7
O1—C3—H3A	109.6	C8—C14—H14	104.7
C2—C3—H3A	109.6	C13—C14—H14	104.7
C4—C3—H3A	109.6	C20—C15—C14	120.9 (3)
C3—C4—C5	115.8 (3)	C20—C15—C16	60.7 (2)
C3—C4—H4A	108.3	C14—C15—C16	105.2 (2)
C5—C4—H4A	108.3	C20—C15—H15	118.2
C3—C4—H4B	108.3	C14—C15—H15	118.2
C5—C4—H4B	108.3	C16—C15—H15	118.2
H4A—C4—H4B	107.4	C17—C16—C20	118.7 (3)
O3—C5—C6	106.5 (2)	C17—C16—C15	107.3 (2)
O3—C5—C4	108.0 (2)	C20—C16—C15	58.02 (19)
C6—C5—C4	108.1 (2)	C17—C16—H16	118.9
O3—C5—C10	110.3 (2)	C20—C16—H16	118.9
C6—C5—C10	111.2 (2)	C15—C16—H16	118.9
C4—C5—C10	112.4 (2)	O4—C17—C16	125.1 (3)
C7—C6—C5	125.2 (3)	O4—C17—C13	125.8 (3)
C7—C6—H6	117.4	C16—C17—C13	109.0 (2)
C5—C6—H6	117.4	C13—C18—H18A	109.5
C6—C7—C8	123.0 (2)	C13—C18—H18B	109.5
C6—C7—H7	118.5	H18A—C18—H18B	109.5
C8—C7—H7	118.5	C13—C18—H18C	109.5
C7—C8—C14	114.3 (2)	H18A—C18—H18C	109.5
C7—C8—C9	110.6 (2)	H18B—C18—H18C	109.5
C14—C8—C9	106.03 (19)	C10—C19—H19A	109.5
C7—C8—H8	108.6	C10—C19—H19B	109.5
C14—C8—H8	108.6	H19A—C19—H19B	109.5
C9—C8—H8	108.6	C10—C19—H19C	109.5
C11—C9—C8	111.9 (2)	H19A—C19—H19C	109.5
C11—C9—C10	115.4 (2)	H19B—C19—H19C	109.5
C8—C9—C10	110.1 (2)	C15—C20—C16	61.3 (2)
C11—C9—H9	106.2	C15—C20—H20A	117.6
C8—C9—H9	106.2	C16—C20—H20A	117.6
C10—C9—H9	106.2	C15—C20—H20B	117.6
C1—C10—C19	107.9 (2)	C16—C20—H20B	117.6
C1—C10—C9	112.2 (2)	H20A—C20—H20B	114.7
C19—C10—C9	110.4 (2)	O2—C21—O1	122.9 (3)
C1—C10—C5	109.3 (2)	O2—C21—C22	124.9 (3)
C19—C10—C5	110.0 (2)	O1—C21—C22	112.1 (3)
C9—C10—C5	106.9 (2)	C21—C22—H22A	109.5
C9—C11—C12	113.1 (2)	C21—C22—H22B	109.5
C9—C11—H11A	109.0	H22A—C22—H22B	109.5
C12—C11—H11A	109.0	C21—C22—H22C	109.5
C9—C11—H11B	109.0	H22A—C22—H22C	109.5
C12—C11—H11B	109.0	H22B—C22—H22C	109.5

C10—C1—C2—C3	57.5 (3)	C8—C9—C11—C12	53.0 (3)
C21—O1—C3—C2	93.8 (4)	C10—C9—C11—C12	−180.0 (2)
C21—O1—C3—C4	−145.3 (3)	C9—C11—C12—C13	−54.7 (3)
C1—C2—C3—O1	65.6 (3)	C11—C12—C13—C17	170.8 (3)
C1—C2—C3—C4	−52.8 (3)	C11—C12—C13—C18	−68.0 (3)
O1—C3—C4—C5	−69.1 (3)	C11—C12—C13—C14	59.7 (3)
C2—C3—C4—C5	50.1 (3)	C7—C8—C14—C15	−44.5 (3)
C3—C4—C5—O3	73.5 (3)	C9—C8—C14—C15	−166.7 (2)
C3—C4—C5—C6	−171.6 (2)	C7—C8—C14—C13	−173.2 (2)
C3—C4—C5—C10	−48.5 (3)	C9—C8—C14—C13	64.7 (2)
O3—C5—C6—C7	−140.1 (3)	C12—C13—C14—C15	155.2 (2)
C4—C5—C6—C7	104.0 (3)	C17—C13—C14—C15	32.5 (3)
C10—C5—C6—C7	−19.9 (4)	C18—C13—C14—C15	−82.6 (3)
C5—C6—C7—C8	4.7 (5)	C12—C13—C14—C8	−67.8 (3)
C6—C7—C8—C14	−139.1 (3)	C17—C13—C14—C8	169.4 (2)
C6—C7—C8—C9	−19.5 (4)	C18—C13—C14—C8	54.3 (3)
C7—C8—C9—C11	179.5 (2)	C8—C14—C15—C20	−88.7 (3)
C14—C8—C9—C11	−56.0 (3)	C13—C14—C15—C20	41.4 (3)
C7—C8—C9—C10	49.7 (3)	C8—C14—C15—C16	−153.3 (2)
C14—C8—C9—C10	174.2 (2)	C13—C14—C15—C16	−23.2 (3)
C2—C1—C10—C19	−173.9 (2)	C20—C15—C16—C17	−113.5 (3)
C2—C1—C10—C9	64.2 (3)	C14—C15—C16—C17	3.7 (3)
C2—C1—C10—C5	−54.3 (3)	C14—C15—C16—C20	117.2 (3)
C11—C9—C10—C1	47.5 (3)	C20—C16—C17—O4	138.3 (3)
C8—C9—C10—C1	175.4 (2)	C15—C16—C17—O4	−159.2 (3)
C11—C9—C10—C19	−73.0 (3)	C20—C16—C17—C13	−44.9 (3)
C8—C9—C10—C19	55.0 (3)	C15—C16—C17—C13	17.6 (3)
C11—C9—C10—C5	167.3 (2)	C12—C13—C17—O4	31.7 (5)
C8—C9—C10—C5	−64.8 (3)	C18—C13—C17—O4	−90.5 (4)
O3—C5—C10—C1	−72.4 (3)	C14—C13—C17—O4	146.2 (3)
C6—C5—C10—C1	169.7 (2)	C12—C13—C17—C16	−145.0 (3)
C4—C5—C10—C1	48.3 (3)	C18—C13—C17—C16	92.7 (3)
O3—C5—C10—C19	46.0 (3)	C14—C13—C17—C16	−30.5 (3)
C6—C5—C10—C19	−72.0 (3)	C14—C15—C20—C16	−90.8 (3)
C4—C5—C10—C19	166.7 (2)	C17—C16—C20—C15	93.3 (3)
O3—C5—C10—C9	165.9 (2)	C3—O1—C21—O2	−0.4 (7)
C6—C5—C10—C9	48.0 (3)	C3—O1—C21—C22	179.7 (3)
C4—C5—C10—C9	−73.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1	0.82	2.27	2.868 (3)	130
C18—H18B···O2ⁱ	0.96	2.55	3.498 (4)	168
C9—H9···O4ⁱⁱ	0.98	2.59	3.542 (3)	165

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₂H₃₀O₄
M_r	358.46
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	7.160 (4), 14.541 (8), 18.733 (10)
V (Å³)	1950.4 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.40 × 0.35 × 0.25

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.957, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	9446, 2437, 2036
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.150, 1.17
No. of reflections	2437
No. of parameters	239
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.26

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Version 1.05; Farrugia, 1997).