19-Benzo­yloxy-13,16-seco-ent-beyeran 13,16-lactone

Cai, J.; Zha, X.

doi:10.1107/S1600536810051561

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page o134

https://doi.org/10.1107/S1600536810051561

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19-Benzoyloxy-13,16-seco-ent-beyeran 13,16-lactone

Jin Cai ^a and Xiaoming Zha ^b ^*

^aInstitute of Pharmaceutical Engineering, School of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China, and ^bJiangsu Center for Drug Screening, China Pharmaceutical University, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: xmzha80@hotmail.com

(Received 30 September 2010; accepted 9 December 2010; online 15 December 2010)

The title compound, C₂₇H₃₄O₅, a beyerane-type diterpenoid prepared by peroxidation and benzoylation of isosteviol, contains a fused six-membered ring system. The O atoms of the benzoic ester and the lactone are disordered with occupancy ratios of 0.6 (4):0.4 (4) and 0.6 (2):0.4 (2), respectively. Three cyclohexane rings have chair conformations, whereas the remaining lactone ring adopts a half-chair conformation.

Related literature

For the pharmaceutical activity of isosteviol, see: Liu et al. (2001 ); Braguini et al. (2003 ); Mizushina et al. (2005 ); Wong et al. (2004); Xu et al. (2007 ). For ring conformations, see: Cremer & Pople (1975 ). For the synthesis of isosteviol derivatives via peroxidation and esterification, see: Chou et al. (2008 ); Wu et al. (2009 ); Chen (2010 ).

Experimental

Crystal data

C₂₇H₃₄O₅
M_r = 438.54
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.7425 (16) Å
b = 11.871 (2) Å
c = 25.306 (5) Å
V = 2325.8 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.48 × 0.46 × 0.43 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.960, T_max = 0.964
12234 measured reflections
2362 independent reflections
1500 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.154
S = 1.03
2362 reflections
310 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810051561/rn2071sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810051561/rn2071Isup2.hkl

checkCIF report

Comment top

Isosteviol, a beyerane-type tetracyclic diterpenoid obtained with stevioside by acid hydrolysis, has a broad spectrum of pharmacological activities against the diseases including hypertension, ischemia-reperfusion injury, and cancer (Wong et al., 2004; Liu et al., 2001; Xu et al., 2007; Mizushina et al., 2005). The title compound was prepared by peroxidation and benzoylation of isosteviol. The molecule contains a fused four-ring system A/B/C/D. The A/B and B/C junctions are trans-fused, and C/D is cis-fused. Six-membered rings A, B and C adopt chair conformations with puckering amplitudes Q = 0.550 (2) / 0.559 (2) / 0.581 (2) Å, θ= 179.6 (2) / 170.4 (3) / 171.8 (3) ° and φ=76 (3) / 76 (2) / 239 (3) °, while the remaining six-membered ring D adopts a half-chair conformation with puckering amplitudes Q = 0.517 (6) Å, θ = 136.0 (3)° and φ= 305 (2) °, respectively (Cremer & Pople, 1975). The bond angle of C8—C15—C14 is 111.5 (4)°. The torsion angle of C1—C2—C3—C4 is -71.8 (6)° relates to the β-orientation of the benzoyl ester group with respect to the ent-kaurane nucleus. The oxygen atoms of the benzoic ester and the lactone are disordered. O1 and O4 are the major components of the disorder. Occupancy ratios of O1/O1' and O4/O4' are 0.6 (4):0.4 (4) and 0.6 (2):0.4 (2), respectively.

Related literature top

For the pharmaceutical activity of isosteviol, see: Liu et al. (2001); Braguini et al. (2003); Mizushina et al. (2005); Wong et al. (2004); Xu et al. (2007). For ring conformations, see: Cremer & Pople (1975). For the synthesis of isosteviol derivatives via peroxidation and esterification, see: Chou et al. (2008); Wu et al. (2009); Chen (2010).

Experimental top

Isosteviol was obtained by acid hydrolysis of stevioside with 10% H₂SO₄ at 95 °C for 7 h and then recrystallization with ethanol afforded colorless crystals of isosteviol in 80% yield. To a mixture of isosteviol (10 g, 31 mmol) in 150 ml of CH₃COOH, 90 ml of 30% H₂O₂ was added and the mixture reaction was stirred at 60°C for two days. The reaction was cooled to room temperature and poured into ice water. The crude product was filtered and purified by recrystallization with ethanol to give the intermediate 13,16-seco-ent-beyeran-19-oate 13,16-lactone (8.2 g, 80%) as white crystals.

To a mixture of 13,16-seco-ent-beyeran-19-oate 13,16-lactone (0.33 g, 0.99 mmol) in 10 ml of CH₂Cl₂, pyridine (0.12 ml, 1.5 mmol) and PhCOCl (0.15 ml, 1.3 mmol) was added successively. The mixture reaction was stirred at room temperature for 40 h and washed with diluted HCl, brine and saturated NaHCO₃ and brine, dried (Na₂SO₄) and concentrated under vacuum to give the crude product. Purification of the crude product by a column chromatography (v:v petroleum ether: EtOAc= 8:1) afforded the title compound (0.28 g, 65%) as colorless crystals. Crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of ethanol solution at room temperature. m.p. 436–437 K; ¹H NMR (300 MHz, CDCl₃), δ_H, p.p.m.: 0.983 (s, 3H), 1.34 (s, 3H), 1.39 (s, 3H), 0.96–2.05 (m, 18H), 2.27–2.32 (d, 1H, J=13.8 Hz), 3.03–3.13 (dd, 1H, J = 18.59, 2.47 Hz), 7.47–7.52 (t, 2H, J=7.7 Hz), 7.62–7.67 (t, 2H, J=14.9 Hz), 7.99–8.02 (m, 1H); ¹³C NMR (75 MHz, CDCl₃), δ_C, p.p.m.: 14.4, 18.6, 18.8, 19.6, 28.1, 28.3, 34.9, 37.9, 38.0, 38.5, 38.6, 39.8, 43.6, 45.6, 47.8, 55.9, 57.4, 128.9, 129.2, 130.3, 130.3, 134.4, 162.3, 172.2, 172.6.

Structure description top

For the pharmaceutical activity of isosteviol, see: Liu et al. (2001); Braguini et al. (2003); Mizushina et al. (2005); Wong et al. (2004); Xu et al. (2007). For ring conformations, see: Cremer & Pople (1975). For the synthesis of isosteviol derivatives via peroxidation and esterification, see: Chou et al. (2008); Wu et al. (2009); Chen (2010).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. H atoms have been omitted. Displacement ellipsoids are drawn at the 30% probability level.

19-Benzoyloxy-13,16-seco-ent-beyeran 13,16-lactone top

Crystal data top

C₂₇H₃₄O₅	F(000) = 944
M_r = 438.54	D_x = 1.252 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2537 reflections
a = 7.7425 (16) Å	θ = 2.4–20.3°
b = 11.871 (2) Å	µ = 0.09 mm⁻¹
c = 25.306 (5) Å	T = 298 K
V = 2325.8 (8) Å³	Prism, colourless
Z = 4	0.48 × 0.46 × 0.43 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2362 independent reflections
Radiation source: fine-focus sealed tube	1500 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
phi and ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −5→9
T_min = 0.960, T_max = 0.964	k = −14→14
12234 measured reflections	l = −28→30

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)] = 0.051	H-atom parameters constrained
wR(F²) = 0.154	w = 1/[σ²(F_o²) + (0.0594P)² + 1.2539P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2362 reflections	Δρ_max = 0.18 e Å⁻³
310 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.023 (3)

Crystal data top

C₂₇H₃₄O₅	V = 2325.8 (8) Å³
M_r = 438.54	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.7425 (16) Å	µ = 0.09 mm⁻¹
b = 11.871 (2) Å	T = 298 K
c = 25.306 (5) Å	0.48 × 0.46 × 0.43 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2362 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1500 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.964	R_int = 0.064
12234 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.154	H-atom parameters constrained
S = 1.03	Δρ_max = 0.18 e Å⁻³
2362 reflections	Δρ_min = −0.19 e Å⁻³
310 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	Occ. (<1)
O1	0.918 (17)	0.286 (9)	0.376 (4)	0.067 (15)	0.6 (4)
O1'	0.87 (2)	0.259 (13)	0.388 (6)	0.07 (2)	0.4 (4)
O2	0.6430 (6)	0.2441 (3)	0.34276 (13)	0.0755 (11)
O3	0.5237 (5)	0.1873 (3)	0.05672 (13)	0.0754 (11)
O4	0.319 (14)	0.287 (9)	0.0949 (8)	0.087 (15)	0.6 (2)
O4'	0.388 (18)	0.324 (8)	0.0979 (18)	0.083 (18)	0.4 (2)
O5	0.8077 (6)	0.4534 (3)	0.37365 (15)	0.0865 (12)
C1	0.7924 (8)	0.2203 (4)	0.34546 (19)	0.0627 (13)
C2	0.8863 (7)	0.1252 (4)	0.31854 (18)	0.0609 (13)
C3	1.0812 (7)	0.1462 (4)	0.3150 (2)	0.0688 (15)
H3A	1.1236	0.1678	0.3496	0.083*
H3B	1.1379	0.0763	0.3052	0.083*
C4	1.1302 (7)	0.2357 (4)	0.2759 (2)	0.0733 (15)
H4A	1.2551	0.2410	0.2740	0.088*
H4B	1.0863	0.3078	0.2879	0.088*
C5	1.0590 (6)	0.2109 (5)	0.22116 (19)	0.0660 (14)
H5A	1.1146	0.1437	0.2075	0.079*
H5B	1.0879	0.2729	0.1978	0.079*
C6	0.8618 (6)	0.1932 (4)	0.22027 (17)	0.0515 (11)
C7	0.8138 (6)	0.1451 (4)	0.16440 (16)	0.0504 (11)
H7	0.8949	0.0828	0.1589	0.061*
C8	0.6345 (6)	0.0916 (4)	0.15766 (16)	0.0507 (11)
C9	0.5994 (7)	0.0101 (4)	0.20318 (16)	0.0582 (13)
H9A	0.6739	−0.0551	0.1995	0.070*
H9B	0.4808	−0.0157	0.2011	0.070*
C10	0.6299 (7)	0.0636 (4)	0.25735 (17)	0.0585 (13)
H10A	0.5532	0.1275	0.2619	0.070*
H10B	0.6049	0.0092	0.2849	0.070*
C11	0.8170 (7)	0.1023 (4)	0.26179 (17)	0.0533 (12)
H11	0.8832	0.0365	0.2502	0.064*
C12	0.8501 (7)	0.2262 (4)	0.11891 (16)	0.0631 (13)
H12A	0.7699	0.2888	0.1206	0.076*
H12B	0.9662	0.2560	0.1224	0.076*
C13	0.8323 (7)	0.1673 (4)	0.06560 (19)	0.0689 (15)
H13A	0.8412	0.2232	0.0378	0.083*
H13B	0.9274	0.1149	0.0613	0.083*
C14	0.6646 (7)	0.1041 (4)	0.05918 (18)	0.0647 (13)
C15	0.6338 (7)	0.0269 (4)	0.10523 (17)	0.0596 (12)
H15A	0.7231	−0.0304	0.1060	0.072*
H15B	0.5234	−0.0105	0.1009	0.072*
C16	0.4840 (7)	0.1744 (4)	0.15308 (18)	0.0590 (13)
H16A	0.3798	0.1352	0.1638	0.071*
H16B	0.5033	0.2343	0.1785	0.071*
C17	0.4497 (8)	0.2280 (5)	0.1007 (2)	0.0706 (15)
C18	0.8566 (9)	0.0239 (4)	0.35505 (19)	0.0830 (18)
H18A	0.9122	−0.0413	0.3405	0.124*
H18B	0.7349	0.0100	0.3582	0.124*
H18C	0.9040	0.0397	0.3893	0.124*
C19	0.6557 (9)	0.0447 (5)	0.00632 (19)	0.0854 (18)
H19A	0.6759	0.0980	−0.0215	0.128*
H19B	0.5434	0.0116	0.0020	0.128*
H19C	0.7420	−0.0133	0.0050	0.128*
C20	0.8505 (8)	0.3784 (5)	0.4017 (2)	0.0704 (14)
C21	0.8676 (7)	0.3817 (4)	0.45931 (19)	0.0642 (13)
C22	0.9247 (8)	0.2913 (5)	0.4883 (2)	0.0811 (17)
H22	0.9533	0.2242	0.4714	0.097*
C23	0.9396 (9)	0.3002 (6)	0.5427 (3)	0.0920 (19)
H23	0.9784	0.2391	0.5624	0.110*
C24	0.8976 (8)	0.3980 (6)	0.5672 (2)	0.0895 (19)
H24	0.9076	0.4035	0.6037	0.107*
C25	0.8411 (9)	0.4880 (6)	0.5388 (2)	0.0886 (18)
H25	0.8135	0.5547	0.5561	0.106*
C26	0.8243 (7)	0.4813 (5)	0.4848 (2)	0.0743 (15)
H26	0.7844	0.5428	0.4656	0.089*
C27	0.7749 (7)	0.3072 (3)	0.23161 (18)	0.0611 (13)
H27A	0.8062	0.3602	0.2046	0.092*
H27B	0.8125	0.3348	0.2654	0.092*
H27C	0.6518	0.2978	0.2319	0.092*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.07 (2)	0.064 (16)	0.067 (14)	0.010 (18)	−0.005 (16)	−0.014 (14)
O1'	0.07 (3)	0.06 (2)	0.07 (2)	0.01 (3)	0.00 (2)	−0.01 (2)
O2	0.075 (3)	0.083 (2)	0.069 (2)	0.005 (2)	0.016 (2)	−0.0057 (19)
O3	0.084 (3)	0.085 (2)	0.058 (2)	0.016 (2)	0.005 (2)	0.0064 (19)
O4	0.08 (2)	0.08 (2)	0.097 (6)	0.03 (2)	−0.006 (8)	0.007 (8)
O4'	0.08 (3)	0.08 (2)	0.091 (9)	0.03 (2)	0.004 (12)	0.011 (10)
O5	0.098 (3)	0.083 (3)	0.078 (2)	0.014 (3)	−0.003 (2)	0.007 (2)
C1	0.071 (4)	0.059 (3)	0.057 (3)	0.007 (3)	−0.001 (3)	−0.002 (3)
C2	0.071 (3)	0.053 (3)	0.059 (3)	0.007 (3)	−0.001 (3)	−0.003 (2)
C3	0.069 (4)	0.065 (3)	0.072 (3)	0.014 (3)	−0.011 (3)	−0.013 (3)
C4	0.063 (3)	0.074 (3)	0.084 (4)	−0.001 (3)	−0.001 (3)	−0.017 (3)
C5	0.059 (3)	0.066 (3)	0.073 (3)	−0.008 (3)	0.009 (3)	−0.003 (3)
C6	0.052 (3)	0.047 (3)	0.055 (3)	0.000 (2)	0.008 (2)	−0.002 (2)
C7	0.054 (3)	0.048 (2)	0.049 (2)	0.002 (2)	0.010 (2)	−0.002 (2)
C8	0.053 (3)	0.047 (2)	0.051 (3)	0.001 (2)	0.009 (2)	0.002 (2)
C9	0.063 (3)	0.051 (3)	0.061 (3)	−0.011 (2)	0.006 (2)	0.005 (2)
C10	0.065 (3)	0.055 (3)	0.056 (3)	−0.006 (3)	0.008 (3)	0.012 (2)
C11	0.059 (3)	0.046 (2)	0.055 (3)	0.003 (2)	0.003 (2)	0.000 (2)
C12	0.070 (3)	0.063 (3)	0.056 (3)	−0.008 (3)	0.014 (3)	0.001 (2)
C13	0.075 (4)	0.078 (3)	0.054 (3)	−0.002 (3)	0.016 (3)	−0.001 (3)
C14	0.067 (3)	0.073 (3)	0.054 (3)	0.005 (3)	0.011 (3)	−0.003 (3)
C15	0.061 (3)	0.059 (3)	0.059 (3)	0.005 (3)	0.007 (3)	−0.009 (2)
C16	0.060 (3)	0.064 (3)	0.053 (3)	0.007 (3)	0.009 (2)	0.001 (2)
C17	0.076 (4)	0.073 (4)	0.063 (3)	0.017 (3)	0.007 (3)	0.004 (3)
C18	0.116 (5)	0.065 (3)	0.068 (3)	0.011 (4)	−0.011 (4)	0.011 (3)
C19	0.088 (4)	0.107 (4)	0.061 (3)	0.001 (4)	0.008 (3)	−0.019 (3)
C20	0.071 (4)	0.071 (4)	0.069 (3)	0.011 (3)	−0.004 (3)	−0.015 (3)
C21	0.061 (3)	0.067 (3)	0.065 (3)	0.003 (3)	−0.002 (3)	−0.014 (3)
C22	0.085 (4)	0.080 (4)	0.079 (4)	0.005 (4)	−0.011 (3)	−0.012 (3)
C23	0.091 (5)	0.098 (5)	0.087 (4)	−0.002 (4)	−0.010 (4)	0.004 (4)
C24	0.077 (4)	0.116 (5)	0.076 (4)	−0.001 (4)	0.000 (4)	−0.014 (4)
C25	0.082 (4)	0.096 (4)	0.088 (4)	0.004 (4)	0.003 (4)	−0.031 (4)
C26	0.069 (4)	0.077 (3)	0.076 (4)	0.005 (3)	−0.001 (3)	−0.018 (3)
C27	0.077 (3)	0.045 (3)	0.062 (3)	0.003 (3)	0.007 (3)	0.002 (2)

Geometric parameters (Å, º) top

O1—C20	1.38 (2)	C10—H10B	0.9700
O1—C1	1.47 (9)	C11—H11	0.9800
O1'—C1	1.31 (4)	C12—C13	1.526 (6)
O1'—C20	1.47 (10)	C12—H12A	0.9700
O2—C1	1.193 (6)	C12—H12B	0.9700
O3—C17	1.341 (6)	C13—C14	1.509 (7)
O3—C14	1.473 (6)	C13—H13A	0.9700
O4—C17	1.24 (3)	C13—H13B	0.9700
O4'—C17	1.24 (4)	C14—C15	1.501 (6)
O5—C20	1.185 (6)	C14—C19	1.514 (6)
C1—C2	1.505 (7)	C15—H15A	0.9700
C2—C3	1.532 (8)	C15—H15B	0.9700
C2—C18	1.534 (6)	C16—C17	1.495 (7)
C2—C11	1.557 (6)	C16—H16A	0.9700
C3—C4	1.501 (7)	C16—H16B	0.9700
C3—H3A	0.9700	C18—H18A	0.9600
C3—H3B	0.9700	C18—H18B	0.9600
C4—C5	1.519 (7)	C18—H18C	0.9600
C4—H4A	0.9700	C19—H19A	0.9600
C4—H4B	0.9700	C19—H19B	0.9600
C5—C6	1.541 (6)	C19—H19C	0.9600
C5—H5A	0.9700	C20—C21	1.465 (7)
C5—H5B	0.9700	C21—C22	1.373 (7)
C6—C27	1.538 (6)	C21—C26	1.389 (7)
C6—C11	1.546 (6)	C22—C23	1.386 (8)
C6—C7	1.569 (6)	C22—H22	0.9300
C7—C12	1.526 (6)	C23—C24	1.355 (9)
C7—C8	1.537 (7)	C23—H23	0.9300
C7—H7	0.9800	C24—C25	1.359 (8)
C8—C9	1.528 (6)	C24—H24	0.9300
C8—C16	1.529 (6)	C25—C26	1.375 (7)
C8—C15	1.533 (6)	C25—H25	0.9300
C9—C10	1.529 (6)	C26—H26	0.9300
C9—H9A	0.9700	C27—H27A	0.9600
C9—H9B	0.9700	C27—H27B	0.9600
C10—C11	1.524 (7)	C27—H27C	0.9600
C10—H10A	0.9700

C20—O1—C1	115 (6)	H12A—C12—H12B	108.0
C1—O1'—C20	119 (6)	C14—C13—C12	113.6 (4)
C17—O3—C14	121.5 (4)	C14—C13—H13A	108.8
O2—C1—O1'	113 (6)	C12—C13—H13A	108.8
O2—C1—O1	123 (2)	C14—C13—H13B	108.8
O1'—C1—O1	23 (6)	C12—C13—H13B	108.8
O2—C1—C2	128.4 (5)	H13A—C13—H13B	107.7
O1'—C1—C2	115 (3)	O3—C14—C15	109.0 (4)
O1—C1—C2	108 (2)	O3—C14—C13	108.0 (4)
C1—C2—C3	112.4 (4)	C15—C14—C13	110.9 (4)
C1—C2—C18	104.0 (4)	O3—C14—C19	104.0 (4)
C3—C2—C18	108.1 (5)	C15—C14—C19	113.2 (4)
C1—C2—C11	112.4 (4)	C13—C14—C19	111.5 (5)
C3—C2—C11	108.3 (4)	C14—C15—C8	111.5 (4)
C18—C2—C11	111.5 (4)	C14—C15—H15A	109.3
C4—C3—C2	113.8 (5)	C8—C15—H15A	109.3
C4—C3—H3A	108.8	C14—C15—H15B	109.3
C2—C3—H3A	108.8	C8—C15—H15B	109.3
C4—C3—H3B	108.8	H15A—C15—H15B	108.0
C2—C3—H3B	108.8	C17—C16—C8	118.5 (4)
H3A—C3—H3B	107.7	C17—C16—H16A	107.7
C3—C4—C5	111.8 (4)	C8—C16—H16A	107.7
C3—C4—H4A	109.3	C17—C16—H16B	107.7
C5—C4—H4A	109.3	C8—C16—H16B	107.7
C3—C4—H4B	109.3	H16A—C16—H16B	107.1
C5—C4—H4B	109.3	O4—C17—O4'	32.7 (15)
H4A—C4—H4B	107.9	O4—C17—O3	117.0 (11)
C4—C5—C6	113.5 (4)	O4'—C17—O3	116.7 (14)
C4—C5—H5A	108.9	O4—C17—C16	119 (2)
C6—C5—H5A	108.9	O4'—C17—C16	121 (2)
C4—C5—H5B	108.9	O3—C17—C16	120.4 (5)
C6—C5—H5B	108.9	C2—C18—H18A	109.5
H5A—C5—H5B	107.7	C2—C18—H18B	109.5
C27—C6—C5	108.1 (4)	H18A—C18—H18B	109.5
C27—C6—C11	112.9 (4)	C2—C18—H18C	109.5
C5—C6—C11	107.9 (4)	H18A—C18—H18C	109.5
C27—C6—C7	112.6 (4)	H18B—C18—H18C	109.5
C5—C6—C7	107.3 (4)	C14—C19—H19A	109.5
C11—C6—C7	107.8 (3)	C14—C19—H19B	109.5
C12—C7—C8	110.1 (4)	H19A—C19—H19B	109.5
C12—C7—C6	114.0 (4)	C14—C19—H19C	109.5
C8—C7—C6	117.7 (4)	H19A—C19—H19C	109.5
C12—C7—H7	104.5	H19B—C19—H19C	109.5
C8—C7—H7	104.5	O5—C20—O1	115 (5)
C6—C7—H7	104.5	O5—C20—C21	127.0 (5)
C9—C8—C16	109.2 (4)	O1—C20—C21	117 (4)
C9—C8—C15	109.6 (3)	O5—C20—O1'	128 (4)
C16—C8—C15	104.7 (4)	O1—C20—O1'	24 (2)
C9—C8—C7	109.8 (4)	C21—C20—O1'	105 (6)
C16—C8—C7	115.5 (4)	C22—C21—C26	119.7 (5)
C15—C8—C7	107.8 (4)	C22—C21—C20	122.7 (5)
C8—C9—C10	112.7 (4)	C26—C21—C20	117.6 (5)
C8—C9—H9A	109.1	C21—C22—C23	119.8 (6)
C10—C9—H9A	109.1	C21—C22—H22	120.1
C8—C9—H9B	109.1	C23—C22—H22	120.1
C10—C9—H9B	109.1	C24—C23—C22	120.0 (6)
H9A—C9—H9B	107.8	C24—C23—H23	120.0
C11—C10—C9	109.7 (4)	C22—C23—H23	120.0
C11—C10—H10A	109.7	C23—C24—C25	120.6 (6)
C9—C10—H10A	109.7	C23—C24—H24	119.7
C11—C10—H10B	109.7	C25—C24—H24	119.7
C9—C10—H10B	109.7	C24—C25—C26	120.6 (6)
H10A—C10—H10B	108.2	C24—C25—H25	119.7
C10—C11—C6	112.0 (4)	C26—C25—H25	119.7
C10—C11—C2	116.6 (4)	C25—C26—C21	119.2 (6)
C6—C11—C2	115.3 (4)	C25—C26—H26	120.4
C10—C11—H11	103.6	C21—C26—H26	120.4
C6—C11—H11	103.6	C6—C27—H27A	109.5
C2—C11—H11	103.6	C6—C27—H27B	109.5
C13—C12—C7	111.2 (4)	H27A—C27—H27B	109.5
C13—C12—H12A	109.4	C6—C27—H27C	109.5
C7—C12—H12A	109.4	H27A—C27—H27C	109.5
C13—C12—H12B	109.4	H27B—C27—H27C	109.5
C7—C12—H12B	109.4

C20—O1'—C1—O2	−51 (23)	C18—C2—C11—C10	53.1 (6)
C20—O1'—C1—O1	68 (18)	C1—C2—C11—C6	71.1 (6)
C20—O1'—C1—C2	148 (12)	C3—C2—C11—C6	−53.7 (6)
C20—O1—C1—O2	0 (15)	C18—C2—C11—C6	−172.5 (4)
C20—O1—C1—O1'	−73 (11)	C8—C7—C12—C13	−55.7 (5)
C20—O1—C1—C2	178 (8)	C6—C7—C12—C13	169.6 (4)
O2—C1—C2—C3	159.0 (5)	C7—C12—C13—C14	51.1 (6)
O1'—C1—C2—C3	−44 (13)	C17—O3—C14—C15	34.9 (6)
O1—C1—C2—C3	−19 (7)	C17—O3—C14—C13	−85.6 (6)
O2—C1—C2—C18	−84.3 (7)	C17—O3—C14—C19	155.9 (5)
O1'—C1—C2—C18	73 (13)	C12—C13—C14—O3	68.0 (5)
O1—C1—C2—C18	97 (7)	C12—C13—C14—C15	−51.3 (6)
O2—C1—C2—C11	36.5 (7)	C12—C13—C14—C19	−178.4 (4)
O1'—C1—C2—C11	−166 (13)	O3—C14—C15—C8	−61.8 (5)
O1—C1—C2—C11	−142 (7)	C13—C14—C15—C8	56.8 (5)
C1—C2—C3—C4	−71.8 (6)	C19—C14—C15—C8	−177.0 (5)
C18—C2—C3—C4	174.0 (4)	C9—C8—C15—C14	178.9 (4)
C11—C2—C3—C4	53.0 (5)	C16—C8—C15—C14	61.9 (5)
C2—C3—C4—C5	−55.2 (6)	C7—C8—C15—C14	−61.6 (5)
C3—C4—C5—C6	55.2 (6)	C9—C8—C16—C17	−154.6 (4)
C4—C5—C6—C27	69.4 (5)	C15—C8—C16—C17	−37.3 (6)
C4—C5—C6—C11	−53.0 (5)	C7—C8—C16—C17	81.1 (5)
C4—C5—C6—C7	−168.9 (4)	C14—O3—C17—O4	−171 (7)
C27—C6—C7—C12	54.5 (5)	C14—O3—C17—O4'	152 (9)
C5—C6—C7—C12	−64.3 (5)	C14—O3—C17—C16	−11.8 (8)
C11—C6—C7—C12	179.7 (4)	C8—C16—C17—O4	173 (7)
C27—C6—C7—C8	−76.6 (5)	C8—C16—C17—O4'	−149 (9)
C5—C6—C7—C8	164.5 (4)	C8—C16—C17—O3	13.9 (8)
C11—C6—C7—C8	48.5 (5)	C1—O1—C20—O5	−70 (13)
C12—C7—C8—C9	179.7 (4)	C1—O1—C20—C21	121 (7)
C6—C7—C8—C9	−47.4 (5)	C1—O1—C20—O1'	58 (11)
C12—C7—C8—C16	−56.3 (5)	C1—O1'—C20—O5	−18 (26)
C6—C7—C8—C16	76.6 (5)	C1—O1'—C20—O1	−83 (19)
C12—C7—C8—C15	60.4 (4)	C1—O1'—C20—C21	152 (17)
C6—C7—C8—C15	−166.7 (4)	O5—C20—C21—C22	−177.4 (6)
C16—C8—C9—C10	−76.2 (5)	O1—C20—C21—C22	−9 (8)
C15—C8—C9—C10	169.7 (4)	O1'—C20—C21—C22	12 (9)
C7—C8—C9—C10	51.4 (5)	O5—C20—C21—C26	2.3 (10)
C8—C9—C10—C11	−60.0 (5)	O1—C20—C21—C26	170 (8)
C9—C10—C11—C6	61.9 (5)	O1'—C20—C21—C26	−168 (9)
C9—C10—C11—C2	−162.2 (4)	C26—C21—C22—C23	−0.4 (9)
C27—C6—C11—C10	70.7 (5)	C20—C21—C22—C23	179.4 (6)
C5—C6—C11—C10	−169.9 (4)	C21—C22—C23—C24	0.1 (10)
C7—C6—C11—C10	−54.3 (5)	C22—C23—C24—C25	−0.1 (10)
C27—C6—C11—C2	−65.8 (6)	C23—C24—C25—C26	0.4 (10)
C5—C6—C11—C2	53.6 (5)	C24—C25—C26—C21	−0.7 (10)
C7—C6—C11—C2	169.2 (4)	C22—C21—C26—C25	0.6 (9)
C1—C2—C11—C10	−63.3 (6)	C20—C21—C26—C25	−179.1 (6)
C3—C2—C11—C10	171.9 (4)

Experimental details

Crystal data
Chemical formula	C₂₇H₃₄O₅
M_r	438.54
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	7.7425 (16), 11.871 (2), 25.306 (5)
V (Å³)	2325.8 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.48 × 0.46 × 0.43

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.960, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	12234, 2362, 1500
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.154, 1.03
No. of reflections	2362
No. of parameters	310
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

We are grateful to the China Ministry of Health Foundation for Scientific Research (project No. WKJ2005–2-022) for financial support.

References

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