Ethoxy­carbonyl­methyl ursolate

Yang, W.; Luo, H.; Yang, C.; Yin, S.; Li, Y.

doi:10.1107/S1600536808039706

Ethoxycarbonylmethyl ursolate

W. Yang, H. Luo, C. Yang, S. Yin and Y. Li

The title compound, C₃₄H₅₄O₅, was synthesized by the reaction of ursolic acid with ethyl chloroacetate in the presence of DMA. All six-membered rings of the pentacyclic triterpene skeleton adopt chair conformations. In the crystal structure, molecules are linked by intermolecular O—H

O hydrogen-bond interactions, forming zigzag chains along the c axis.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808039706/rz2269sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808039706/rz2269Isup2.hkl Contains datablock I

CCDC reference: 712580

checkCIF report

Key indicators

Single-crystal X-ray study
T = 292 K
Mean (C-C) = 0.005 Å
R factor = 0.047
wR factor = 0.125
Data-to-parameter ratio = 8.6

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   292.000
            Value of melting point given =     0.000
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.53 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.05 Ratio
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5
PLAT234_ALERT_4_C Large Hirshfeld Difference O4     --  C33     ..       0.11  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C3     --  C7      ..       0.11  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C4     --  C5      ..       0.10  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C13    --  C18     ..       0.10  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C15    --  C20     ..       0.13  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C22    --  C30     ..       0.11  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C24    --  C25     ..       0.12  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C33    --  C34     ..       0.13  Ang.

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           25.24
           From the CIF: _reflns_number_total               3116
           Count of symmetry unique reflns         3173
           Completeness (_total/calc)             98.20%
           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_4_G The Model has Chirality at C1      (Verify) ....          R
PLAT791_ALERT_4_G The Model has Chirality at C2      (Verify) ....          R
PLAT791_ALERT_4_G The Model has Chirality at C4      (Verify) ....          S
PLAT791_ALERT_4_G The Model has Chirality at C12     (Verify) ....          R
PLAT791_ALERT_4_G The Model has Chirality at C13     (Verify) ....          S
PLAT791_ALERT_4_G The Model has Chirality at C15     (Verify) ....          S
PLAT791_ALERT_4_G The Model has Chirality at C22     (Verify) ....          S
PLAT791_ALERT_4_G The Model has Chirality at C23     (Verify) ....          S
PLAT791_ALERT_4_G The Model has Chirality at C24     (Verify) ....          S
PLAT791_ALERT_4_G The Model has Chirality at C25     (Verify) ....          R

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

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

Comment top

Ursolic acid, a pentacyclic triterpene existing abundantly in the plant kingdom, has been reported to possess pharmacological activities, such as anti-tumor, anti-inflammatory and anti-HIV activities (Es-saady et al., 1996; Kashiwada et al., 2000). The synthesis and characterization of some derivatives of this compound have been recently reported (Liu et al., 2007). We report herein the crystal structure of the title compound, whose synthetic method has been already reported elsewhere (Yang et al., 2008).

In the molecule of the title compound (Fig.1) bond lengths and angles within the six-membered rings are very similar to those given in the literature for ursolic acid (Simon et al., 1992). The C(sp²)—C(sp²) bond distance (C16—C17) is 1.317 (5) Å, the C(sp³)—C(sp³) bond lengths range from 1.506 (6) Å to 1.592 (5) Å, and the three C(sp³)—C(sp²) bond distances (C17—C18, C16—C23 and C16—C15) are 1.491 (5), 1.528 (5) and 1.545 (5) Å, respectively. The five six-membered rings adopt a chair conformation. The carboxy group at C22 and the methyl groups C7, C9, C14 and C19 are axially oriented, while the hydroxy groups and the methyl groups C8, C28 and C29 are in equatorial positions. The O2–C30–C22–C27 and C2–C30–C22–C21 torsion angles are -72.1 (4) Å and 47.8 Å, respectively. In the crystal packing, intermolecular O—H···O hydrogen bonds (Table 1) link molecules to form zig-zag chains extending along the c axis.

Related literature top

For the pharmacological activities of ursolic acid, see: Es-saady et al. (1996); Kashiwada et al. (2000). For the crystal structure of ursolic acid, see: Simon et al. (1992). For the synthesis and characterization of the title compound and other ursoic acid derivatives, see: Yang et al. (2008); Liu et al. (2007).

Experimental top

To a solution of ursolid acid (456 mg, 1 mmol) in DMF (10 ml) was added K₂CO₃ (300 mg, 2.2 mmol), KI (50 mg, 0.3 mmol) and NEt₃ (0.5 ml). After stirring at room temperature for 10 minutes, a solution of ethyl chlorocetate (0.4 ml, 3 mmol) in DMF was added dropwise, and the reaction monitored by TLC. After completion of the reaction, satured brines and ehtyl acetate were added. The organic layer was separated, washed with water until neutral, dried with Na₂SO₄, filtered and evaporated in vacuo to get the solid title compound. Colourless crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature.

Computing details top

Data collection: DIFRAC (Gabe & White, 1993); cell refinement: DIFRAC (Gabe & White, 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.

Ethoxycarbonylmethyl ursolate top

Crystal data top

C₃₄H₅₄O₅	F(000) = 1192
M_r = 542.77	D_x = 1.158 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 14 reflections
a = 11.624 (3) Å	θ = 4.3–5.6°
b = 12.465 (4) Å	µ = 0.08 mm⁻¹
c = 21.478 (3) Å	T = 292 K
V = 3112.0 (14) Å³	Block, colourless
Z = 4	0.60 × 0.56 × 0.44 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.009
Radiation source: fine-focus sealed tube	θ_max = 25.2°, θ_min = 1.9°
Graphite monochromator	h = −2→13
ω/2θ scans	k = −6→14
3435 measured reflections	l = −3→25
3116 independent reflections	3 standard reflections every 200 reflections
1818 reflections with I > 2σ(I)	intensity decay: 0.9%

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)] = 0.047	H-atom parameters constrained
wR(F²) = 0.125	w = 1/[σ²(F_o²) + (0.0695P)²] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max < 0.001
3116 reflections	Δρ_max = 0.19 e Å⁻³
362 parameters	Δρ_min = −0.17 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: 0.0090 (12)

Crystal data top

C₃₄H₅₄O₅	V = 3112.0 (14) Å³
M_r = 542.77	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 11.624 (3) Å	µ = 0.08 mm⁻¹
b = 12.465 (4) Å	T = 292 K
c = 21.478 (3) Å	0.60 × 0.56 × 0.44 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.009
3435 measured reflections	3 standard reflections every 200 reflections
3116 independent reflections	intensity decay: 0.9%
1818 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 0.97	Δρ_max = 0.19 e Å⁻³
3116 reflections	Δρ_min = −0.17 e Å⁻³
362 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 > 2σ(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	0.3112 (2)	−0.0655 (2)	0.43876 (11)	0.0676 (8)
H1	0.2632	−0.1128	0.4442	0.101*
O2	0.5639 (2)	0.28015 (19)	−0.04823 (12)	0.0593 (7)
O3	0.3922 (2)	0.20169 (19)	−0.04048 (12)	0.0554 (7)
O4	0.4470 (3)	0.4876 (2)	−0.14161 (14)	0.0785 (9)
O5	0.4757 (3)	0.3145 (2)	−0.16352 (13)	0.0855 (10)
C1	0.3267 (3)	0.0359 (3)	0.24624 (16)	0.0457 (9)
C2	0.4278 (3)	0.0554 (3)	0.29194 (16)	0.0465 (9)
H2	0.4800	−0.0049	0.2841	0.056*
C3	0.4019 (3)	0.0475 (3)	0.36250 (16)	0.0495 (10)
C4	0.3383 (3)	−0.0584 (3)	0.37360 (17)	0.0516 (10)
H4	0.3922	−0.1166	0.3641	0.062*
C5	0.2331 (4)	−0.0748 (3)	0.33319 (18)	0.0597 (11)
H5A	0.1764	−0.0201	0.3425	0.072*
H5B	0.1993	−0.1443	0.3421	0.072*
C6	0.2661 (3)	−0.0687 (3)	0.26447 (16)	0.0527 (10)
H6A	0.1970	−0.0764	0.2395	0.063*
H6B	0.3164	−0.1285	0.2547	0.063*
C7	0.3321 (4)	0.1428 (3)	0.38858 (18)	0.0654 (11)
H7A	0.2538	0.1374	0.3749	0.098*
H7B	0.3647	0.2089	0.3738	0.098*
H7C	0.3346	0.1414	0.4333	0.098*
C8	0.5167 (4)	0.0419 (3)	0.39817 (19)	0.0649 (12)
H8A	0.5018	0.0303	0.4416	0.097*
H8B	0.5578	0.1081	0.3929	0.097*
H8C	0.5622	−0.0163	0.3822	0.097*
C9	0.2352 (4)	0.1256 (3)	0.24777 (19)	0.0648 (12)
H9A	0.1847	0.1145	0.2825	0.097*
H9B	0.1915	0.1242	0.2099	0.097*
H9C	0.2726	0.1939	0.2519	0.097*
C10	0.4969 (4)	0.1536 (3)	0.27172 (17)	0.0579 (11)
H10A	0.5552	0.1693	0.3027	0.069*
H10B	0.4461	0.2152	0.2688	0.069*
C11	0.5544 (3)	0.1341 (3)	0.20874 (16)	0.0537 (10)
H11A	0.6105	0.0770	0.2132	0.064*
H11B	0.5955	0.1985	0.1966	0.064*
C12	0.4692 (3)	0.1036 (3)	0.15636 (17)	0.0478 (9)
C13	0.3811 (3)	0.0197 (3)	0.18028 (16)	0.0472 (9)
H13	0.4251	−0.0471	0.1837	0.057*
C14	0.4064 (4)	0.2061 (3)	0.13466 (18)	0.0583 (11)
H14A	0.3572	0.1892	0.1001	0.087*
H14B	0.4620	0.2588	0.1221	0.087*
H14C	0.3610	0.2341	0.1683	0.087*
C15	0.5377 (3)	0.0506 (3)	0.10000 (17)	0.0472 (9)
C16	0.4504 (3)	0.0129 (2)	0.05037 (16)	0.0450 (9)
C17	0.3432 (3)	−0.0089 (3)	0.06576 (17)	0.0521 (10)
H17	0.2946	−0.0305	0.0337	0.063*
C18	0.2915 (3)	−0.0026 (3)	0.12919 (18)	0.0597 (11)
H18A	0.2528	−0.0697	0.1383	0.072*
H18B	0.2342	0.0540	0.1297	0.072*
C19	0.6073 (4)	−0.0486 (3)	0.12069 (19)	0.0615 (11)
H19A	0.5554	−0.1046	0.1332	0.092*
H19B	0.6559	−0.0297	0.1551	0.092*
H19C	0.6538	−0.0734	0.0867	0.092*
C20	0.6231 (3)	0.1324 (3)	0.07259 (18)	0.0599 (11)
H20A	0.5860	0.2021	0.0712	0.072*
H20B	0.6886	0.1381	0.1004	0.072*
C21	0.6667 (3)	0.1052 (3)	0.00753 (17)	0.0597 (11)
H21A	0.7111	0.0394	0.0091	0.072*
H21B	0.7168	0.1621	−0.0071	0.072*
C22	0.5655 (3)	0.0913 (3)	−0.03835 (17)	0.0495 (10)
C23	0.4897 (3)	−0.0026 (3)	−0.01690 (16)	0.0482 (9)
H23	0.4199	0.0008	−0.0424	0.058*
C24	0.5438 (4)	−0.1142 (3)	−0.02978 (18)	0.0640 (12)
H24	0.6126	−0.1207	−0.0037	0.077*
C25	0.5818 (4)	−0.1250 (3)	−0.0978 (2)	0.0719 (13)
H25	0.5131	−0.1206	−0.1241	0.086*
C26	0.6616 (4)	−0.0351 (4)	−0.1159 (2)	0.0772 (14)
H26A	0.6821	−0.0427	−0.1595	0.093*
H26B	0.7317	−0.0403	−0.0916	0.093*
C27	0.6083 (4)	0.0742 (3)	−0.10584 (18)	0.0615 (11)
H27A	0.5440	0.0829	−0.1342	0.074*
H27B	0.6647	0.1290	−0.1157	0.074*
C28	0.6415 (5)	−0.2339 (4)	−0.1107 (2)	0.114 (2)
H28A	0.6680	−0.2357	−0.1530	0.171*
H28B	0.5878	−0.2912	−0.1040	0.171*
H28C	0.7058	−0.2422	−0.0830	0.171*
C29	0.4606 (4)	−0.2040 (3)	−0.0109 (2)	0.0799 (14)
H29A	0.3923	−0.1998	−0.0359	0.120*
H29B	0.4406	−0.1962	0.0322	0.120*
H29C	0.4969	−0.2724	−0.0173	0.120*
C30	0.4959 (4)	0.1934 (3)	−0.04108 (16)	0.0479 (9)
C31	0.5087 (4)	0.3793 (3)	−0.06002 (19)	0.0600 (11)
H31A	0.5601	0.4377	−0.0491	0.072*
H31B	0.4404	0.3851	−0.0343	0.072*
C32	0.4757 (4)	0.3882 (4)	−0.1274 (2)	0.0605 (11)
C33	0.4120 (5)	0.5073 (4)	−0.2062 (2)	0.0857 (15)
H33A	0.4706	0.4813	−0.2346	0.103*
H33B	0.3407	0.4698	−0.2151	0.103*
C34	0.3961 (6)	0.6224 (4)	−0.2142 (2)	0.1113 (19)
H34A	0.3488	0.6497	−0.1812	0.167*
H34B	0.3593	0.6359	−0.2535	0.167*
H34C	0.4696	0.6575	−0.2134	0.167*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.076 (2)	0.083 (2)	0.0439 (16)	−0.0207 (18)	0.0043 (15)	0.0021 (13)
O2	0.0541 (16)	0.0551 (16)	0.0687 (18)	−0.0096 (14)	0.0000 (15)	0.0092 (13)
O3	0.0504 (17)	0.0527 (15)	0.0631 (18)	−0.0007 (14)	0.0040 (15)	0.0057 (13)
O4	0.100 (2)	0.0616 (18)	0.074 (2)	0.0112 (19)	−0.0051 (18)	0.0084 (15)
O5	0.124 (3)	0.073 (2)	0.0590 (18)	0.004 (2)	0.009 (2)	0.0028 (16)
C1	0.044 (2)	0.043 (2)	0.050 (2)	−0.0025 (19)	−0.0064 (19)	−0.0030 (16)
C2	0.049 (2)	0.0384 (19)	0.052 (2)	−0.0028 (19)	−0.002 (2)	−0.0017 (16)
C3	0.051 (2)	0.054 (2)	0.044 (2)	0.000 (2)	0.002 (2)	−0.0035 (17)
C4	0.053 (2)	0.053 (2)	0.049 (2)	−0.004 (2)	−0.001 (2)	0.0001 (18)
C5	0.060 (3)	0.061 (3)	0.057 (2)	−0.019 (2)	0.007 (2)	−0.004 (2)
C6	0.052 (2)	0.057 (2)	0.048 (2)	−0.015 (2)	−0.001 (2)	−0.0026 (18)
C7	0.073 (3)	0.062 (2)	0.062 (3)	−0.008 (2)	0.008 (2)	−0.013 (2)
C8	0.064 (3)	0.079 (3)	0.051 (2)	−0.012 (2)	−0.008 (2)	0.000 (2)
C9	0.066 (3)	0.063 (3)	0.065 (3)	0.010 (2)	−0.012 (2)	−0.004 (2)
C10	0.064 (3)	0.054 (2)	0.056 (2)	−0.014 (2)	−0.003 (2)	−0.0048 (19)
C11	0.049 (2)	0.058 (2)	0.054 (2)	−0.015 (2)	0.000 (2)	−0.0023 (18)
C12	0.048 (2)	0.046 (2)	0.049 (2)	−0.0072 (19)	−0.0035 (19)	0.0031 (17)
C13	0.041 (2)	0.046 (2)	0.055 (2)	−0.0082 (18)	−0.0107 (18)	−0.0003 (18)
C14	0.065 (3)	0.050 (2)	0.060 (2)	−0.005 (2)	0.002 (2)	0.0080 (19)
C15	0.043 (2)	0.045 (2)	0.053 (2)	−0.0041 (19)	−0.0038 (19)	0.0013 (18)
C16	0.050 (2)	0.0393 (19)	0.046 (2)	−0.0048 (19)	−0.0056 (19)	0.0028 (17)
C17	0.051 (3)	0.055 (2)	0.050 (2)	−0.013 (2)	−0.010 (2)	0.0068 (18)
C18	0.052 (2)	0.073 (3)	0.054 (3)	−0.016 (2)	−0.004 (2)	0.004 (2)
C19	0.059 (3)	0.067 (3)	0.058 (3)	0.006 (2)	−0.011 (2)	0.003 (2)
C20	0.049 (2)	0.078 (3)	0.053 (3)	−0.010 (2)	−0.009 (2)	−0.002 (2)
C21	0.046 (2)	0.069 (3)	0.064 (3)	−0.005 (2)	−0.001 (2)	0.003 (2)
C22	0.049 (2)	0.053 (2)	0.047 (2)	0.000 (2)	−0.004 (2)	0.0011 (17)
C23	0.045 (2)	0.052 (2)	0.048 (2)	0.0040 (19)	−0.0065 (19)	0.0016 (17)
C24	0.073 (3)	0.058 (2)	0.062 (3)	0.020 (2)	−0.017 (2)	−0.0056 (19)
C25	0.067 (3)	0.067 (3)	0.081 (3)	0.022 (3)	−0.015 (3)	−0.018 (2)
C26	0.064 (3)	0.100 (4)	0.068 (3)	0.014 (3)	0.008 (3)	−0.020 (3)
C27	0.051 (2)	0.076 (3)	0.057 (3)	0.001 (2)	0.006 (2)	−0.001 (2)
C28	0.129 (5)	0.093 (3)	0.121 (5)	0.045 (4)	0.004 (4)	−0.029 (3)
C29	0.103 (4)	0.050 (2)	0.087 (3)	0.002 (3)	−0.017 (3)	0.001 (2)
C30	0.049 (3)	0.059 (2)	0.035 (2)	−0.008 (2)	0.003 (2)	0.0008 (18)
C31	0.073 (3)	0.047 (2)	0.060 (3)	−0.008 (2)	0.003 (2)	0.0049 (19)
C32	0.062 (3)	0.055 (3)	0.064 (3)	−0.007 (2)	0.010 (2)	0.006 (2)
C33	0.090 (4)	0.105 (4)	0.063 (3)	0.018 (3)	−0.001 (3)	0.021 (3)
C34	0.142 (5)	0.093 (4)	0.100 (4)	0.030 (4)	0.009 (4)	0.036 (3)

Geometric parameters (Å, º) top

O1—C4	1.437 (4)	C15—C19	1.543 (5)
O1—H1	0.8200	C15—C16	1.545 (5)
O2—C30	1.348 (4)	C16—C17	1.317 (5)
O2—C31	1.415 (4)	C16—C23	1.528 (5)
O3—C30	1.210 (4)	C17—C18	1.491 (5)
O4—C32	1.319 (5)	C17—H17	0.9300
O4—C33	1.466 (5)	C18—H18A	0.9700
O5—C32	1.203 (5)	C18—H18B	0.9700
C1—C6	1.533 (5)	C19—H19A	0.9600
C1—C9	1.543 (5)	C19—H19B	0.9600
C1—C2	1.551 (5)	C19—H19C	0.9600
C1—C13	1.565 (5)	C20—C21	1.525 (5)
C2—C10	1.527 (5)	C20—H20A	0.9700
C2—C3	1.548 (5)	C20—H20B	0.9700
C2—H2	0.9800	C21—C22	1.544 (5)
C3—C4	1.531 (5)	C21—H21A	0.9700
C3—C8	1.540 (5)	C21—H21B	0.9700
C3—C7	1.544 (5)	C22—C30	1.510 (5)
C4—C5	1.513 (5)	C22—C23	1.535 (5)
C4—H4	0.9800	C22—C27	1.547 (5)
C5—C6	1.527 (5)	C23—C24	1.552 (5)
C5—H5A	0.9700	C23—H23	0.9800
C5—H5B	0.9700	C24—C25	1.531 (6)
C6—H6A	0.9700	C24—C29	1.534 (6)
C6—H6B	0.9700	C24—H24	0.9800
C7—H7A	0.9600	C25—C26	1.506 (6)
C7—H7B	0.9600	C25—C28	1.550 (5)
C7—H7C	0.9600	C25—H25	0.9800
C8—H8A	0.9600	C26—C27	1.512 (5)
C8—H8B	0.9600	C26—H26A	0.9700
C8—H8C	0.9600	C26—H26B	0.9700
C9—H9A	0.9600	C27—H27A	0.9700
C9—H9B	0.9600	C27—H27B	0.9700
C9—H9C	0.9600	C28—H28A	0.9600
C10—C11	1.528 (5)	C28—H28B	0.9600
C10—H10A	0.9700	C28—H28C	0.9600
C10—H10B	0.9700	C29—H29A	0.9600
C11—C12	1.546 (5)	C29—H29B	0.9600
C11—H11A	0.9700	C29—H29C	0.9600
C11—H11B	0.9700	C31—C32	1.501 (6)
C12—C14	1.544 (5)	C31—H31A	0.9700
C12—C13	1.551 (5)	C31—H31B	0.9700
C12—C15	1.592 (5)	C33—C34	1.457 (6)
C13—C18	1.538 (5)	C33—H33A	0.9700
C13—H13	0.9800	C33—H33B	0.9700
C14—H14A	0.9600	C34—H34A	0.9600
C14—H14B	0.9600	C34—H34B	0.9600
C14—H14C	0.9600	C34—H34C	0.9600
C15—C20	1.541 (5)

C4—O1—H1	109.5	C18—C17—H17	116.6
C30—O2—C31	117.1 (3)	C17—C18—C13	112.9 (3)
C32—O4—C33	116.5 (4)	C17—C18—H18A	109.0
C6—C1—C9	107.1 (3)	C13—C18—H18A	109.0
C6—C1—C2	108.6 (3)	C17—C18—H18B	109.0
C9—C1—C2	113.3 (3)	C13—C18—H18B	109.0
C6—C1—C13	107.9 (3)	H18A—C18—H18B	107.8
C9—C1—C13	113.1 (3)	C15—C19—H19A	109.5
C2—C1—C13	106.7 (3)	C15—C19—H19B	109.5
C10—C2—C3	115.6 (3)	H19A—C19—H19B	109.5
C10—C2—C1	110.1 (3)	C15—C19—H19C	109.5
C3—C2—C1	117.5 (3)	H19A—C19—H19C	109.5
C10—C2—H2	103.9	H19B—C19—H19C	109.5
C3—C2—H2	103.9	C21—C20—C15	114.7 (3)
C1—C2—H2	103.9	C21—C20—H20A	108.6
C4—C3—C8	107.6 (3)	C15—C20—H20A	108.6
C4—C3—C7	110.7 (3)	C21—C20—H20B	108.6
C8—C3—C7	108.0 (3)	C15—C20—H20B	108.6
C4—C3—C2	107.5 (3)	H20A—C20—H20B	107.6
C8—C3—C2	108.7 (3)	C20—C21—C22	110.9 (3)
C7—C3—C2	114.1 (3)	C20—C21—H21A	109.5
O1—C4—C5	111.9 (3)	C22—C21—H21A	109.5
O1—C4—C3	108.1 (3)	C20—C21—H21B	109.5
C5—C4—C3	114.7 (3)	C22—C21—H21B	109.5
O1—C4—H4	107.3	H21A—C21—H21B	108.1
C5—C4—H4	107.3	C30—C22—C23	110.3 (3)
C3—C4—H4	107.3	C30—C22—C21	109.8 (3)
C4—C5—C6	110.2 (3)	C23—C22—C21	109.3 (3)
C4—C5—H5A	109.6	C30—C22—C27	104.6 (3)
C6—C5—H5A	109.6	C23—C22—C27	111.1 (3)
C4—C5—H5B	109.6	C21—C22—C27	111.6 (3)
C6—C5—H5B	109.6	C16—C23—C22	111.1 (3)
H5A—C5—H5B	108.1	C16—C23—C24	113.8 (3)
C5—C6—C1	113.9 (3)	C22—C23—C24	113.4 (3)
C5—C6—H6A	108.8	C16—C23—H23	105.9
C1—C6—H6A	108.8	C22—C23—H23	105.9
C5—C6—H6B	108.8	C24—C23—H23	105.9
C1—C6—H6B	108.8	C25—C24—C29	111.7 (3)
H6A—C6—H6B	107.7	C25—C24—C23	111.4 (3)
C3—C7—H7A	109.5	C29—C24—C23	110.6 (3)
C3—C7—H7B	109.5	C25—C24—H24	107.6
H7A—C7—H7B	109.5	C29—C24—H24	107.6
C3—C7—H7C	109.5	C23—C24—H24	107.6
H7A—C7—H7C	109.5	C26—C25—C24	111.1 (3)
H7B—C7—H7C	109.5	C26—C25—C28	109.3 (4)
C3—C8—H8A	109.5	C24—C25—C28	112.1 (4)
C3—C8—H8B	109.5	C26—C25—H25	108.1
H8A—C8—H8B	109.5	C24—C25—H25	108.1
C3—C8—H8C	109.5	C28—C25—H25	108.1
H8A—C8—H8C	109.5	C25—C26—C27	112.4 (3)
H8B—C8—H8C	109.5	C25—C26—H26A	109.1
C1—C9—H9A	109.5	C27—C26—H26A	109.1
C1—C9—H9B	109.5	C25—C26—H26B	109.1
H9A—C9—H9B	109.5	C27—C26—H26B	109.1
C1—C9—H9C	109.5	H26A—C26—H26B	107.9
H9A—C9—H9C	109.5	C26—C27—C22	113.0 (3)
H9B—C9—H9C	109.5	C26—C27—H27A	109.0
C2—C10—C11	110.7 (3)	C22—C27—H27A	109.0
C2—C10—H10A	109.5	C26—C27—H27B	109.0
C11—C10—H10A	109.5	C22—C27—H27B	109.0
C2—C10—H10B	109.5	H27A—C27—H27B	107.8
C11—C10—H10B	109.5	C25—C28—H28A	109.5
H10A—C10—H10B	108.1	C25—C28—H28B	109.5
C10—C11—C12	113.7 (3)	H28A—C28—H28B	109.5
C10—C11—H11A	108.8	C25—C28—H28C	109.5
C12—C11—H11A	108.8	H28A—C28—H28C	109.5
C10—C11—H11B	108.8	H28B—C28—H28C	109.5
C12—C11—H11B	108.8	C24—C29—H29A	109.5
H11A—C11—H11B	107.7	C24—C29—H29B	109.5
C14—C12—C11	108.6 (3)	H29A—C29—H29B	109.5
C14—C12—C13	110.3 (3)	C24—C29—H29C	109.5
C11—C12—C13	110.3 (3)	H29A—C29—H29C	109.5
C14—C12—C15	110.5 (3)	H29B—C29—H29C	109.5
C11—C12—C15	109.6 (3)	O3—C30—O2	121.2 (4)
C13—C12—C15	107.6 (3)	O3—C30—C22	127.2 (4)
C18—C13—C12	109.4 (3)	O2—C30—C22	111.5 (3)
C18—C13—C1	113.3 (3)	O2—C31—C32	110.7 (3)
C12—C13—C1	118.7 (3)	O2—C31—H31A	109.5
C18—C13—H13	104.7	C32—C31—H31A	109.5
C12—C13—H13	104.7	O2—C31—H31B	109.5
C1—C13—H13	104.7	C32—C31—H31B	109.5
C12—C14—H14A	109.5	H31A—C31—H31B	108.1
C12—C14—H14B	109.5	O5—C32—O4	124.6 (4)
H14A—C14—H14B	109.5	O5—C32—C31	124.5 (4)
C12—C14—H14C	109.5	O4—C32—C31	110.9 (4)
H14A—C14—H14C	109.5	C34—C33—O4	108.2 (4)
H14B—C14—H14C	109.5	C34—C33—H33A	110.1
C20—C15—C19	107.6 (3)	O4—C33—H33A	110.1
C20—C15—C16	111.2 (3)	C34—C33—H33B	110.1
C19—C15—C16	107.4 (3)	O4—C33—H33B	110.1
C20—C15—C12	109.7 (3)	H33A—C33—H33B	108.4
C19—C15—C12	112.1 (3)	C33—C34—H34A	109.5
C16—C15—C12	108.8 (3)	C33—C34—H34B	109.5
C17—C16—C23	119.7 (3)	H34A—C34—H34B	109.5
C17—C16—C15	120.7 (3)	C33—C34—H34C	109.5
C23—C16—C15	119.6 (3)	H34A—C34—H34C	109.5
C16—C17—C18	126.8 (4)	H34B—C34—H34C	109.5
C16—C17—H17	116.6

C6—C1—C2—C10	174.9 (3)	C20—C15—C16—C23	36.8 (4)
C9—C1—C2—C10	−66.1 (4)	C19—C15—C16—C23	−80.7 (4)
C13—C1—C2—C10	58.9 (3)	C12—C15—C16—C23	157.7 (3)
C6—C1—C2—C3	−49.9 (4)	C23—C16—C17—C18	177.5 (3)
C9—C1—C2—C3	69.0 (4)	C15—C16—C17—C18	−0.7 (6)
C13—C1—C2—C3	−165.9 (3)	C16—C17—C18—C13	−7.3 (6)
C10—C2—C3—C4	−177.0 (3)	C12—C13—C18—C17	40.4 (4)
C1—C2—C3—C4	50.2 (4)	C1—C13—C18—C17	175.2 (3)
C10—C2—C3—C8	−60.8 (4)	C19—C15—C20—C21	75.6 (4)
C1—C2—C3—C8	166.4 (3)	C16—C15—C20—C21	−41.8 (4)
C10—C2—C3—C7	59.8 (4)	C12—C15—C20—C21	−162.2 (3)
C1—C2—C3—C7	−73.0 (4)	C15—C20—C21—C22	56.4 (4)
C8—C3—C4—O1	64.5 (4)	C20—C21—C22—C30	59.1 (4)
C7—C3—C4—O1	−53.3 (4)	C20—C21—C22—C23	−62.0 (4)
C2—C3—C4—O1	−178.6 (3)	C20—C21—C22—C27	174.6 (3)
C8—C3—C4—C5	−170.0 (3)	C17—C16—C23—C22	137.4 (4)
C7—C3—C4—C5	72.2 (4)	C15—C16—C23—C22	−44.5 (4)
C2—C3—C4—C5	−53.0 (4)	C17—C16—C23—C24	−93.2 (4)
O1—C4—C5—C6	−179.0 (3)	C15—C16—C23—C24	85.0 (4)
C3—C4—C5—C6	57.5 (4)	C30—C22—C23—C16	−66.1 (4)
C4—C5—C6—C1	−56.1 (4)	C21—C22—C23—C16	54.8 (4)
C9—C1—C6—C5	−71.5 (4)	C27—C22—C23—C16	178.4 (3)
C2—C1—C6—C5	51.2 (4)	C30—C22—C23—C24	164.3 (3)
C13—C1—C6—C5	166.4 (3)	C21—C22—C23—C24	−74.9 (4)
C3—C2—C10—C11	159.2 (3)	C27—C22—C23—C24	48.8 (4)
C1—C2—C10—C11	−64.7 (4)	C16—C23—C24—C25	−179.9 (4)
C2—C10—C11—C12	56.7 (4)	C22—C23—C24—C25	−51.7 (4)
C10—C11—C12—C14	76.7 (4)	C16—C23—C24—C29	55.2 (4)
C10—C11—C12—C13	−44.3 (4)	C22—C23—C24—C29	−176.5 (3)
C10—C11—C12—C15	−162.5 (3)	C29—C24—C25—C26	178.9 (3)
C14—C12—C13—C18	55.5 (4)	C23—C24—C25—C26	54.6 (5)
C11—C12—C13—C18	175.4 (3)	C29—C24—C25—C28	−58.6 (5)
C15—C12—C13—C18	−65.1 (4)	C23—C24—C25—C28	177.2 (4)
C14—C12—C13—C1	−76.6 (4)	C24—C25—C26—C27	−56.9 (5)
C11—C12—C13—C1	43.4 (4)	C28—C25—C26—C27	178.9 (4)
C15—C12—C13—C1	162.9 (3)	C25—C26—C27—C22	55.1 (5)
C6—C1—C13—C18	62.5 (4)	C30—C22—C27—C26	−169.3 (3)
C9—C1—C13—C18	−55.8 (4)	C23—C22—C27—C26	−50.2 (5)
C2—C1—C13—C18	179.1 (3)	C21—C22—C27—C26	72.1 (4)
C6—C1—C13—C12	−167.1 (3)	C31—O2—C30—O3	−5.0 (5)
C9—C1—C13—C12	74.6 (4)	C31—O2—C30—C22	171.6 (3)
C2—C1—C13—C12	−50.6 (4)	C23—C22—C30—O3	−15.3 (5)
C14—C12—C15—C20	57.2 (4)	C21—C22—C30—O3	−135.9 (4)
C11—C12—C15—C20	−62.4 (4)	C27—C22—C30—O3	104.2 (4)
C13—C12—C15—C20	177.6 (3)	C23—C22—C30—O2	168.3 (3)
C14—C12—C15—C19	176.7 (3)	C21—C22—C30—O2	47.8 (4)
C11—C12—C15—C19	57.1 (4)	C27—C22—C30—O2	−72.1 (4)
C13—C12—C15—C19	−62.8 (4)	C30—O2—C31—C32	−80.2 (4)
C14—C12—C15—C16	−64.7 (3)	C33—O4—C32—O5	0.6 (7)
C11—C12—C15—C16	175.7 (3)	C33—O4—C32—C31	−179.6 (4)
C13—C12—C15—C16	55.8 (3)	O2—C31—C32—O5	13.2 (6)
C20—C15—C16—C17	−145.1 (4)	O2—C31—C32—O4	−166.6 (3)
C19—C15—C16—C17	97.4 (4)	C32—O4—C33—C34	−173.9 (4)
C12—C15—C16—C17	−24.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.82	2.14	2.944 (4)	165

Symmetry code: (i) −x+1/2, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	C₃₄H₅₄O₅
M_r	542.77
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	292
a, b, c (Å)	11.624 (3), 12.465 (4), 21.478 (3)
V (Å³)	3112.0 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.60 × 0.56 × 0.44

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3435, 3116, 1818
R_int	0.009
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.125, 0.97
No. of reflections	3116
No. of parameters	362
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.17

Computer programs: DIFRAC (Gabe & White, 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).