3β-Acet­oxy-17-ethyl­enedioxy­androst-5-ene

Xu, Y.-M.; Tang, S.-G.; Zhou, Y.-X.; Liu, S.; Guo, C.

doi:10.1107/S160053680703944X

3β-Acetoxy-17-ethylenedioxyandrost-5-ene

Y.-M. Xu, S.-G. Tang, Y.-X. Zhou, S. Liu and C. Guo

In the molecule of the title compound, C₂₃H₃₄O₄, the six-membered rings A, B and C have chair, flattened boat and chair conformations, respectively, while the two five-membered rings D and E have envelope conformations. Intramolecular C—H

O hydrogen bonds result in the formation of three more five-membered rings.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703944X/hk2310sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680703944X/hk2310Isup2.hkl Contains datablock I

CCDC reference: 663705

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.010 Å
R factor = 0.078
wR factor = 0.199
Data-to-parameter ratio = 9.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.72 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.45 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O1
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C20
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C25
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C3
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         10

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           25.98
           From the CIF: _reflns_number_total               2189
           Count of symmetry unique reflns         2191
           Completeness (_total/calc)             99.91%
           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
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C7     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C10    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C11    = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C16    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C17    = .          S
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         62

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

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

Comment top

The title compound, (I), is an intermediate product of drospirenone, which is a new oral contraceptive (Mohr & Nickisch, 2005). We report herein its crystal structure.

In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987).

Rings A (C4—C9), B (C7/C8/C10—C13) and C (C10/C11/C14—C17) are not planar, having total puckering amplitudes, Q_T, of 0.547 (3), 0.477 (2) and 0.676 (3) Å, respectively, and chair, flattened boat and chair conformations, respectively [φ = -173.98 (3)°, θ = 169.83 (3)°; φ = -16.01 (2)°, θ = 115.71 (3)° and φ = -147.03 (3)°, θ = 86.92 (3)°, respectively] (Cremer & Pople, 1975). Rings D (C16/C17/C19—C21) and E (O3/O4/C19/C24/C25) have envelope conformations with atoms C16 and C19 displaced by 0.646 (3) Å and 0.220 (2) Å from the planes of the other four ring atoms, respectively. Rings D and E have pseudo twofold axis and pseudo mirror plane, respectively, running through atom C20 and midpoint of C16—C17 bond (for ring D) and atom C19 and midpoint of C24—C25 bond (for ring E), as can be deduced from the torsion angles (Table 1).

The intramolecular C—H···O hydrogen bonds (Table 2, Fig. 1) result in the formation of three more five-membered rings F (O1/O2/C3/C4/H4A), G (C15/C16/C19/O4/H15A) and H (O3/C16/C19/C23/H23B), in which they may be effective in the stabilization of the structure.

As can be seen from the packing diagram (Fig. 2), the molecules of (I) are elongated along the c axis, and stacked along the a axis. Dipole-dipole and van der Waals interactions may be effective in the molecular packing.

Related literature top

For related literature, see: Mohr & Nickisch (2005); Kelly & Sykes (1968). For general background, see: Cremer & Pople (1975). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I), was prepared by a literature method (Kelly & Sykes, 1968). The crystals were obtained by dissolving (I) (1.0 g, 2.5 mmol) in methanol (50 ml), and evaporating the solvent slowly at room temperature for about 15 d.

Structure description top

The title compound, (I), is an intermediate product of drospirenone, which is a new oral contraceptive (Mohr & Nickisch, 2005). We report herein its crystal structure.

In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987).

For related literature, see: Mohr & Nickisch (2005); Kelly & Sykes (1968). For general background, see: Cremer & Pople (1975). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top

	Fig. 1. A drawing of the title molecular structure, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Intramolecular hydrogen bonds are shown as dashed lines.
	Fig. 2. A packing diagram for (I). Intramolecular hydrogen bonds are shown as dashed lines.

3β-Acetoxy-17-ethylenedioxyandrost-5-ene top

Crystal data top

C₂₃H₃₄O₄	F(000) = 816
M_r = 374.50	D_x = 1.207 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 25 reflections
a = 10.197 (2) Å	θ = 9–12°
b = 7.5370 (15) Å	µ = 0.08 mm⁻¹
c = 27.143 (5) Å	T = 298 K
β = 99.04 (3)°	Block, colorless
V = 2060.2 (7) Å³	0.40 × 0.30 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1420 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.065
Graphite monochromator	θ_max = 26.0°, θ_min = 1.5°
ω/2θ scans	h = −12→12
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
T_min = 0.976, T_max = 0.990	l = 0→33
2324 measured reflections	3 standard reflections every 120 min
2189 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.199	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.06P)² + 5P] where P = (F_o² + 2F_c²)/3
2189 reflections	(Δ/σ)_max = 0.012
227 parameters	Δρ_max = 0.48 e Å⁻³
62 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₂₃H₃₄O₄	V = 2060.2 (7) Å³
M_r = 374.50	Z = 4
Monoclinic, C2	Mo Kα radiation
a = 10.197 (2) Å	µ = 0.08 mm⁻¹
b = 7.5370 (15) Å	T = 298 K
c = 27.143 (5) Å	0.40 × 0.30 × 0.10 mm
β = 99.04 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1420 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.065
T_min = 0.976, T_max = 0.990	3 standard reflections every 120 min
2324 measured reflections	intensity decay: none
2189 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.078	62 restraints
wR(F²) = 0.199	H-atom parameters constrained
S = 1.04	Δρ_max = 0.48 e Å⁻³
2189 reflections	Δρ_min = −0.33 e Å⁻³
227 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	−0.1505 (5)	−0.0998 (10)	0.05652 (17)	0.095 (2)
O2	−0.3488 (7)	−0.0028 (10)	0.0652 (2)	0.109
O3	0.3844 (5)	0.0504 (10)	0.44585 (17)	0.0851 (18)
O4	0.1664 (4)	0.1086 (8)	0.42607 (16)	0.0675 (14)
C2	−0.3092 (10)	−0.0908 (17)	−0.0154 (3)	0.108
H2A	−0.2345	−0.0601	−0.0312	0.162*
H2B	−0.3834	−0.0169	−0.0282	0.162*
H2C	−0.3321	−0.2129	−0.0220	0.162*
C3	−0.2745 (8)	−0.0634 (13)	0.0394 (3)	0.078 (2)
C4	−0.1026 (7)	−0.0719 (15)	0.1084 (2)	0.078 (3)
H4A	−0.1720	−0.0156	0.1242	0.094*
C5	−0.0628 (8)	−0.2437 (12)	0.1339 (2)	0.069 (2)
H5A	0.0052	−0.2996	0.1179	0.083*
H5B	−0.1389	−0.3225	0.1304	0.083*
C6	−0.0101 (7)	−0.2169 (11)	0.1891 (2)	0.0611 (19)
H6A	0.0189	−0.3306	0.2036	0.073*
H6B	−0.0822	−0.1754	0.2055	0.073*
C7	0.1070 (6)	−0.0832 (10)	0.1997 (2)	0.0470 (16)
C8	0.0725 (6)	0.0808 (9)	0.1667 (2)	0.0465 (15)
C9	0.0181 (7)	0.0490 (11)	0.1131 (2)	0.0637 (19)
H9A	0.0859	−0.0052	0.0966	0.076*
H9B	−0.0067	0.1613	0.0968	0.076*
C10	0.1242 (5)	−0.0273 (8)	0.2554 (2)	0.0393 (13)
H10A	0.0351	−0.0008	0.2627	0.047*
C11	0.2064 (6)	0.1409 (9)	0.2669 (2)	0.0449 (15)
H11A	0.2946	0.1220	0.2579	0.054*
C12	0.1398 (6)	0.2947 (10)	0.2366 (2)	0.0528 (16)
H12A	0.0666	0.3378	0.2521	0.063*
H12B	0.2031	0.3907	0.2366	0.063*
C13	0.0893 (6)	0.2431 (10)	0.1843 (2)	0.0538 (17)
H13A	0.0671	0.3350	0.1616	0.065*
C14	0.1793 (7)	−0.1834 (10)	0.2906 (2)	0.0566 (18)
H14A	0.1186	−0.2830	0.2848	0.068*
H14B	0.2640	−0.2211	0.2822	0.068*
C15	0.1978 (7)	−0.1332 (10)	0.3463 (2)	0.0550 (17)
H15A	0.1117	−0.1110	0.3560	0.066*
H15B	0.2387	−0.2314	0.3661	0.066*
C16	0.2849 (6)	0.0321 (9)	0.3568 (2)	0.0473 (15)
C17	0.2215 (5)	0.1801 (8)	0.3228 (2)	0.0434 (14)
H17A	0.1308	0.1918	0.3301	0.052*
C19	0.2886 (6)	0.1226 (11)	0.4089 (3)	0.0588 (17)
C20	0.3178 (8)	0.3188 (13)	0.3994 (3)	0.076 (2)
H20A	0.4092	0.3464	0.4131	0.092*
H20B	0.2602	0.3943	0.4154	0.092*
C21	0.2937 (7)	0.3518 (11)	0.3427 (3)	0.0630 (19)
H21A	0.2385	0.4555	0.3342	0.076*
H21B	0.3767	0.3664	0.3299	0.076*
C22	0.2318 (6)	−0.1720 (12)	0.1853 (2)	0.066 (2)
H22A	0.2554	−0.2731	0.2063	0.099*
H22B	0.3039	−0.0886	0.1894	0.099*
H22C	0.2137	−0.2094	0.1511	0.099*
C23	0.4290 (6)	−0.0059 (12)	0.3500 (3)	0.068 (2)
H23A	0.4298	−0.0641	0.3186	0.102*
H23B	0.4702	−0.0810	0.3766	0.102*
H23C	0.4771	0.1038	0.3506	0.102*
C24	0.1802 (8)	−0.0145 (15)	0.4659 (3)	0.088 (3)
H24A	0.1344	−0.1244	0.4556	0.105*
H24B	0.1445	0.0336	0.4942	0.105*
C25	0.3240 (9)	−0.0442 (17)	0.4786 (4)	0.103
H25B	0.3553	−0.0051	0.5125	0.123*
H25A	0.3440	−0.1694	0.4763	0.123*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.080 (4)	0.156 (6)	0.043 (3)	0.023 (4)	−0.014 (2)	−0.027 (4)
O2	0.109	0.109	0.109	0.000	0.017	0.000
O3	0.056 (2)	0.141 (5)	0.052 (3)	0.003 (3)	−0.012 (2)	0.003 (3)
O4	0.057 (2)	0.104 (4)	0.044 (2)	0.006 (3)	0.0146 (19)	−0.004 (3)
C2	0.108	0.108	0.108	0.000	0.017	0.000
C3	0.069 (4)	0.100 (6)	0.056 (4)	0.010 (4)	−0.020 (3)	0.000 (4)
C4	0.063 (4)	0.132 (8)	0.037 (4)	0.015 (5)	0.000 (3)	−0.015 (5)
C5	0.075 (5)	0.087 (6)	0.047 (4)	−0.024 (5)	0.012 (3)	−0.026 (4)
C6	0.064 (4)	0.067 (5)	0.052 (4)	−0.010 (4)	0.009 (3)	−0.018 (4)
C7	0.043 (3)	0.069 (4)	0.030 (3)	0.003 (3)	0.009 (2)	0.002 (3)
C8	0.047 (3)	0.058 (4)	0.035 (3)	0.000 (3)	0.008 (2)	−0.003 (3)
C9	0.074 (5)	0.072 (5)	0.045 (4)	−0.003 (4)	0.007 (3)	−0.004 (4)
C10	0.038 (3)	0.047 (3)	0.035 (3)	0.002 (3)	0.009 (2)	−0.004 (3)
C11	0.037 (3)	0.066 (4)	0.033 (3)	0.001 (3)	0.010 (2)	−0.004 (3)
C12	0.054 (4)	0.060 (4)	0.045 (4)	0.001 (3)	0.011 (3)	−0.001 (3)
C13	0.054 (4)	0.066 (5)	0.041 (4)	0.006 (4)	0.005 (3)	0.011 (3)
C14	0.064 (4)	0.058 (4)	0.046 (4)	−0.008 (4)	0.004 (3)	0.006 (3)
C15	0.062 (4)	0.052 (4)	0.051 (4)	−0.004 (3)	0.007 (3)	0.010 (3)
C16	0.046 (3)	0.057 (4)	0.038 (3)	0.001 (3)	0.005 (3)	−0.003 (3)
C17	0.033 (3)	0.050 (4)	0.047 (3)	0.003 (3)	0.008 (2)	0.000 (3)
C19	0.045 (3)	0.076 (5)	0.056 (4)	0.001 (3)	0.007 (3)	−0.003 (3)
C20	0.075 (5)	0.094 (7)	0.058 (4)	−0.014 (5)	0.002 (4)	−0.027 (5)
C21	0.060 (4)	0.065 (5)	0.062 (4)	−0.009 (4)	0.005 (3)	−0.007 (4)
C22	0.065 (4)	0.090 (6)	0.045 (4)	0.022 (4)	0.013 (3)	−0.001 (4)
C23	0.044 (3)	0.095 (6)	0.065 (4)	0.005 (4)	0.011 (3)	0.001 (4)
C24	0.080 (4)	0.117 (6)	0.067 (4)	−0.015 (5)	0.014 (4)	0.008 (4)
C25	0.103	0.103	0.103	0.000	0.016	0.000

Geometric parameters (Å, º) top

O1—C3	1.307 (8)	C12—C13	1.483 (9)
O1—C4	1.432 (7)	C12—H12A	0.9700
O4—C19	1.402 (8)	C12—H12B	0.9700
O4—C24	1.414 (10)	C13—H13A	0.9300
O3—C25	1.361 (11)	C14—C15	1.540 (8)
O3—C19	1.396 (8)	C14—H14A	0.9700
O2—C3	1.201 (10)	C14—H14B	0.9700
C2—C3	1.487 (11)	C15—C16	1.530 (9)
C2—H2A	0.9600	C15—H15A	0.9700
C2—H2B	0.9600	C15—H15B	0.9700
C2—H2C	0.9600	C16—C17	1.526 (9)
C4—C5	1.494 (13)	C16—C23	1.537 (8)
C4—C9	1.521 (11)	C16—C19	1.564 (9)
C4—H4A	0.9800	C17—C21	1.544 (10)
C5—C6	1.523 (9)	C17—H17A	0.9800
C5—H5A	0.9700	C19—C20	1.538 (12)
C5—H5B	0.9700	C20—C21	1.539 (10)
C6—C7	1.555 (9)	C20—H20A	0.9700
C6—H6A	0.9700	C20—H20B	0.9700
C6—H6B	0.9700	C21—H21A	0.9700
C7—C8	1.535 (9)	C21—H21B	0.9700
C7—C22	1.542 (8)	C22—H22A	0.9600
C7—C10	1.552 (7)	C22—H22B	0.9600
C8—C13	1.314 (10)	C22—H22C	0.9600
C8—C9	1.494 (8)	C23—H23A	0.9600
C9—H9A	0.9700	C23—H23B	0.9600
C9—H9B	0.9700	C23—H23C	0.9600
C10—C11	1.525 (8)	C24—C25	1.470 (11)
C10—C14	1.563 (9)	C24—H24A	0.9700
C10—H10A	0.9800	C24—H24B	0.9700
C11—C12	1.519 (9)	C25—H25B	0.9700
C11—C17	1.528 (8)	C25—H25A	0.9700
C11—H11A	0.9800

C3—O1—C4	118.7 (6)	C15—C14—C10	113.0 (6)
C19—O4—C24	108.5 (6)	C15—C14—H14A	109.0
C25—O3—C19	109.7 (6)	C10—C14—H14A	109.0
C3—C2—H2A	109.5	C15—C14—H14B	109.0
C3—C2—H2B	109.5	C10—C14—H14B	109.0
H2A—C2—H2B	109.5	H14A—C14—H14B	107.8
C3—C2—H2C	109.5	C16—C15—C14	111.2 (5)
H2A—C2—H2C	109.5	C16—C15—H15A	109.4
H2B—C2—H2C	109.5	C14—C15—H15A	109.4
O2—C3—O1	122.4 (7)	C16—C15—H15B	109.4
O2—C3—C2	124.4 (8)	C14—C15—H15B	109.4
O1—C3—C2	113.1 (8)	H15A—C15—H15B	108.0
O1—C4—C5	110.7 (8)	C15—C16—C17	107.7 (5)
O1—C4—C9	108.5 (7)	C15—C16—C23	111.3 (6)
C5—C4—C9	108.9 (6)	C17—C16—C23	112.7 (5)
O1—C4—H4A	109.6	C15—C16—C19	117.1 (5)
C5—C4—H4A	109.6	C17—C16—C19	100.2 (5)
C9—C4—H4A	109.6	C23—C16—C19	107.6 (5)
C4—C5—C6	111.7 (7)	C16—C17—C11	115.3 (5)
C4—C5—H5A	109.3	C16—C17—C21	105.5 (5)
C6—C5—H5A	109.3	C11—C17—C21	118.6 (5)
C4—C5—H5B	109.3	C16—C17—H17A	105.5
C6—C5—H5B	109.3	C11—C17—H17A	105.5
H5A—C5—H5B	108.0	C21—C17—H17A	105.5
C5—C6—C7	114.3 (6)	O3—C19—O4	106.8 (6)
C5—C6—H6A	108.7	O3—C19—C20	111.3 (7)
C7—C6—H6A	108.7	O4—C19—C20	109.5 (6)
C5—C6—H6B	108.7	O3—C19—C16	113.2 (6)
C7—C6—H6B	108.7	O4—C19—C16	111.8 (5)
H6A—C6—H6B	107.6	C20—C19—C16	104.2 (6)
C8—C7—C22	108.9 (5)	C19—C20—C21	108.6 (6)
C8—C7—C10	109.3 (5)	C19—C20—H20A	110.0
C22—C7—C10	113.2 (5)	C21—C20—H20A	110.0
C8—C7—C6	108.4 (5)	C19—C20—H20B	110.0
C22—C7—C6	108.2 (6)	C21—C20—H20B	110.0
C10—C7—C6	108.9 (5)	H20A—C20—H20B	108.4
C13—C8—C9	120.7 (6)	C17—C21—C20	102.0 (6)
C13—C8—C7	122.2 (5)	C17—C21—H21A	111.4
C9—C8—C7	117.1 (6)	C20—C21—H21A	111.4
C8—C9—C4	110.4 (5)	C17—C21—H21B	111.4
C8—C9—H9A	109.6	C20—C21—H21B	111.4
C4—C9—H9A	109.6	H21A—C21—H21B	109.2
C8—C9—H9B	109.6	C7—C22—H22A	109.5
C4—C9—H9B	109.6	C7—C22—H22B	109.5
H9A—C9—H9B	108.1	H22A—C22—H22B	109.5
C11—C10—C7	113.6 (5)	C7—C22—H22C	109.5
C11—C10—C14	111.5 (4)	H22A—C22—H22C	109.5
C7—C10—C14	111.4 (5)	H22B—C22—H22C	109.5
C11—C10—H10A	106.6	C16—C23—H23A	109.5
C7—C10—H10A	106.6	C16—C23—H23B	109.5
C14—C10—H10A	106.6	H23A—C23—H23B	109.5
C12—C11—C10	109.8 (5)	C16—C23—H23C	109.5
C12—C11—C17	111.0 (5)	H23A—C23—H23C	109.5
C10—C11—C17	109.3 (5)	H23B—C23—H23C	109.5
C12—C11—H11A	108.9	O4—C24—C25	104.8 (7)
C10—C11—H11A	108.9	O4—C24—H24A	110.8
C17—C11—H11A	108.9	C25—C24—H24A	110.8
C13—C12—C11	112.2 (6)	O4—C24—H24B	110.8
C13—C12—H12A	109.2	C25—C24—H24B	110.8
C11—C12—H12A	109.2	H24A—C24—H24B	108.9
C13—C12—H12B	109.2	O3—C25—C24	107.7 (8)
C11—C12—H12B	109.2	O3—C25—H25B	110.2
H12A—C12—H12B	107.9	C24—C25—H25B	110.2
C8—C13—C12	126.6 (6)	O3—C25—H25A	110.2
C8—C13—H13A	116.7	C24—C25—H25A	110.2
C12—C13—H13A	116.7	H25B—C25—H25A	108.5

C4—O1—C3—O2	2.1 (15)	C14—C15—C16—C17	55.8 (7)
C4—O1—C3—C2	177.4 (10)	C14—C15—C16—C23	−68.2 (7)
C3—O1—C4—C5	115.6 (9)	C14—C15—C16—C19	167.5 (6)
C3—O1—C4—C9	−125.0 (9)	C15—C16—C17—C11	−59.4 (7)
O1—C4—C5—C6	179.4 (5)	C23—C16—C17—C11	63.7 (7)
C9—C4—C5—C6	60.2 (8)	C19—C16—C17—C11	177.7 (5)
C4—C5—C6—C7	−55.3 (9)	C15—C16—C17—C21	167.8 (5)
C5—C6—C7—C8	45.2 (8)	C23—C16—C17—C21	−69.1 (7)
C5—C6—C7—C22	−72.6 (8)	C19—C16—C17—C21	44.9 (6)
C5—C6—C7—C10	163.9 (6)	C12—C11—C17—C16	178.8 (5)
C22—C7—C8—C13	−108.8 (7)	C10—C11—C17—C16	57.6 (6)
C10—C7—C8—C13	15.3 (8)	C12—C11—C17—C21	−54.8 (7)
C6—C7—C8—C13	133.7 (7)	C10—C11—C17—C21	−176.1 (5)
C22—C7—C8—C9	71.3 (7)	C25—O3—C19—O4	14.6 (9)
C10—C7—C8—C9	−164.6 (5)	C25—O3—C19—C20	134.1 (8)
C6—C7—C8—C9	−46.1 (7)	C25—O3—C19—C16	−108.9 (8)
C13—C8—C9—C4	−125.4 (8)	C24—O4—C19—O3	−16.4 (8)
C7—C8—C9—C4	54.4 (8)	C24—O4—C19—C20	−137.0 (7)
O1—C4—C9—C8	−179.5 (6)	C24—O4—C19—C16	108.0 (7)
C5—C4—C9—C8	−58.9 (8)	C15—C16—C19—O3	87.0 (7)
C8—C7—C10—C11	−44.8 (6)	C17—C16—C19—O3	−157.0 (6)
C22—C7—C10—C11	76.7 (7)	C23—C16—C19—O3	−39.1 (8)
C6—C7—C10—C11	−163.0 (5)	C15—C16—C19—O4	−33.7 (8)
C8—C7—C10—C14	−171.8 (5)	C17—C16—C19—O4	82.3 (7)
C22—C7—C10—C14	−50.3 (7)	C23—C16—C19—O4	−159.9 (6)
C6—C7—C10—C14	70.1 (7)	C15—C16—C19—C20	−151.9 (6)
C7—C10—C11—C12	60.1 (6)	C17—C16—C19—C20	−35.9 (6)
C14—C10—C11—C12	−172.9 (5)	C23—C16—C19—C20	82.0 (7)
C7—C10—C11—C17	−177.9 (5)	O3—C19—C20—C21	137.3 (6)
C14—C10—C11—C17	−51.0 (6)	O4—C19—C20—C21	−104.8 (6)
C10—C11—C12—C13	−42.8 (7)	C16—C19—C20—C21	15.0 (8)
C17—C11—C12—C13	−163.8 (5)	C16—C17—C21—C20	−35.8 (7)
C9—C8—C13—C12	178.9 (6)	C11—C17—C21—C20	−166.7 (6)
C7—C8—C13—C12	−0.9 (10)	C19—C20—C21—C17	12.0 (8)
C11—C12—C13—C8	15.1 (10)	C19—O4—C24—C25	11.9 (9)
C11—C10—C14—C15	51.9 (7)	C19—O3—C25—C24	−7.1 (11)
C7—C10—C14—C15	180.0 (5)	O4—C24—C25—O3	−3.0 (11)
C10—C14—C15—C16	−54.5 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O2	0.98	2.22	2.650 (10)	105
C15—H15A···O4	0.97	2.52	2.886 (8)	102
C23—H23B···O3	0.96	2.41	2.744 (9)	100

Experimental details

Crystal data
Chemical formula	C₂₃H₃₄O₄
M_r	374.50
Crystal system, space group	Monoclinic, C2
Temperature (K)	298
a, b, c (Å)	10.197 (2), 7.5370 (15), 27.143 (5)
β (°)	99.04 (3)
V (Å³)	2060.2 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.40 × 0.30 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.976, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	2324, 2189, 1420
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.078, 0.199, 1.04
No. of reflections	2189
No. of parameters	227
No. of restraints	62
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.33

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000).

Selected bond and torsion angles (º) top

O3—C19—O4	106.8 (6)	O4—C19—C16	111.8 (5)
O3—C19—C20	111.3 (7)	O4—C24—C25	104.8 (7)
O4—C19—C20	109.5 (6)	O3—C25—C24	107.7 (8)
O3—C19—C16	113.2 (6)

C19—C16—C17—C21	44.9 (6)	C16—C17—C21—C20	−35.8 (7)
C25—O3—C19—O4	14.6 (9)	C19—C20—C21—C17	12.0 (8)
C24—O4—C19—O3	−16.4 (8)	C19—O4—C24—C25	11.9 (9)
C17—C16—C19—C20	−35.9 (6)	C19—O3—C25—C24	−7.1 (11)
C16—C19—C20—C21	15.0 (8)	O4—C24—C25—O3	−3.0 (11)