(S)-5-(l-Menth­yloxy)-5-[(2R,3R)-2-(l-menth­yloxy)-5-oxotetra­hydro­furan-3-yl]furan-2(5H)-one

Zhang, B.-B.; Fu, Y.-Q.; Tao, J.-C.

doi:10.1107/S1600536809053690

(S)-5-(l-Menthyloxy)-5-[(2R,3R)-2-(l-menthyloxy)-5-oxotetrahydrofuran-3-yl]furan-2(5H)-one

In the title compound, C₂₈H₄₄O₆, the two five-membered rings form a dihedral angle of 6.7 (1)°. In the crystal structure, weak intermolecular C—H

O hydrogen bonds link molecules into layers parallel to (101).

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809053690/cv2674sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536809053690/cv2674Isup2.hkl Contains datablock I

CCDC reference: 766856

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.005 Å
R factor = 0.041
wR factor = 0.107
Data-to-parameter ratio = 9.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.53 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C15
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C25
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          5
PLAT127_ALERT_1_C Implicit Hall Symbol  Inconsistent with Explicit       P 21
PLAT234_ALERT_4_C Large Hirshfeld Difference C25    --  C26     ..       0.16 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           25.50
           From the CIF: _reflns_number_total               2847
           Count of symmetry unique reflns         2851
           Completeness (_total/calc)             99.86%
           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 C4      (Verify) ....          S
PLAT791_ALERT_4_G The Model has Chirality at C7      (Verify) ....          R
PLAT791_ALERT_4_G The Model has Chirality at C8      (Verify) ....          R
PLAT791_ALERT_4_G The Model has Chirality at C9      (Verify) ....          R
PLAT791_ALERT_4_G The Model has Chirality at C10     (Verify) ....          S
PLAT791_ALERT_4_G The Model has Chirality at C13     (Verify) ....          R
PLAT791_ALERT_4_G The Model has Chirality at C19     (Verify) ....          R
PLAT791_ALERT_4_G The Model has Chirality at C20     (Verify) ....          S
PLAT791_ALERT_4_G The Model has Chirality at C23     (Verify) ....          R

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
  11 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The well known chiral 5-(R)-(l-menthyloxy)-2(5H)-furanone behaves as a Michael acceptor towards carbon, oxygen, sulfur and nitrogen nucleophiles to afford chiral 4-(R)-(l-menthyloxy)-3-substituted-butyrolactone (Huang et al., 1999; Wang et al., 1999; Fu et al., 2003; Yu et al., 2008). Recently, when we have used 1,2:5,6-di-O-isopropylidene-D-glucofuranose as Michael donor to react with 5-(R)-(l-menthyloxy)-2(5H)-furanone, the adduct was not yielded, but the title compound, (I) - unexpected product of the self-addition of 5-(R)-(l-menthyloxy)-2(5H)-furanone - was obtained. Herein, we report the synthesis, characterization and crystal structure of (I) (Fig. 1).

In the crystal structure, each molecule is connected by six adjacent molecules through weak intermolecular C—H···O hydrogen bonds (Table 1) between H atoms of menthyloxy groups, or H atoms of lactone, and O atoms of the carbonyl groups, leading to the formation of a two-dimensional sheet parallel to (a+c)b plane (Fig. 2). The layers are further packed through van der Waals forces..

The absolute configuration of the title compound was established on the basis of the chiral l-menthyloxy group. In the addition reaction, the three chiral centers on the l-menthyloxy group did not change because they did not participant in the reaction. Accordingly, the stereogenic center of C7 is determined as R, the configuration of C4 and C8 are retained.

Related literature top

For the applications of 5-(R)-(l-menthyloxy)-2(5H)-furanone in asymmetic synthesis, see: Huang & Chen (1999); Wang & Chen (1999); Fu et al. (2003); Yu et al. (2008).

Experimental top

1,2:5,6-di-O-isopropylidene-α-D-glucofuranose (2 mmol, 0.520 g) was added to the mixture of powdered K₂CO₃ (10 mmol, 1.382 g), tetrabutylammonium bromide (2 mmol, 0.645 g) and acetonitrile (20 ml). The mixture was stirred for 20 minutes, then the chiral synthon 5-(R)-(l-menthyloxy)-2(5H)-furanone (4 mmol, 0.953 g) was added and the mixture was stirred at room temperature for 8 days until TLC analysis indicated that the chiral synthon had been completely consumed. After the addition of acetonitrile (50 ml), the mixture was filtered and the salts were washed with acetonitrile. The organic layer was dried over MgSO₄, evaporated, and purified by column chromatography to give a white solid, which was recrystalized to afford colorless crystal.

Yield 38.8%, m.p. 143–144 °C, [α]_D²⁰: -159 (c 0.1, CHCl₃); IR (KBr, cm^-1): 3096,3079, 2957, 2918, 2872, 1810, 1781, 1768, 1612, 1456, 1384, 1369, 905; ¹HNMR (400 MHz, CDCl₃) δ: 0.68 (d, J = 6.8 Hz, 3H, CH₃,), 0.76 (d, J = 6.8 Hz, 3H, CH₃), 0.83 (d, J = 6.4 Hz, 3H, CH₃,), 0.86 (d, J = 6.4 Hz, 3H,CH₃), 0.91 (d, J = 6.8 Hz, 3H, CH₃), 0.93 (d, J = 6.4 Hz, 3H, CH₃),1.00–1.19 (m, 6H, 6CH), 1.25–1.65 (m, 8H, 4CH₂), 2.03–2.05 (m, 4H, 2CH₂), 2.45 (m, 1H, CH), 2.75–2.82 (m, 2H, 2CH), 3.17–3.20 (m,1H, CH), 3.50–3.53 (m, 1H, CH), 5.65 (d, J = 1.6 Hz, 1H, OCH), 6.36 (d, J = 5.6 Hz, 1H, CH), 7.02 (d, J = 5.6 Hz, 1H, CH); ¹³C NMR (100 MHz, CDCl₃) δ: 15.6, 15.8, 20.9, 21.2,22.1, 22.3, 22.7, 23.1, 25.3, 25.5, 29.5, 31.4, 31.5, 33.9, 34.3, 39.6, 43.4,47.7, 48.2, 49.4, 75.8, 77.4, 100.4, 110.0, 126.6, 150.9, 168.5, 174.4; HRMS (ESI) m/z: calcd. for C₂₈H₄₄O₆ (M+Na⁺) 499.3036, found 499.3035.

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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I) showing the atomic numbering and 20% probability displacement ellipsoids.
	Fig. 2. A portion of the crystal packing showing weak intermolecular C—H···O hydrogen-bonds as dashed lines.

(S)-5-(l-Menthyloxy)-5-[(2R,3R)-2-(l- menthyloxy)-5- oxotetrahydrofuran-3-yl]furan-2(5H)-one top

Crystal data top

C₂₈H₄₄O₆	F(000) = 520
M_r = 476.63	D_x = 1.099 Mg m⁻³
Monoclinic, P2₁	Melting point: 416 K
Hall symbol: P 2y1	Mo Kα radiation, λ = 0.71073 Å
a = 12.3443 (15) Å	Cell parameters from 2076 reflections
b = 9.3455 (11) Å	θ = 2.4–19.9°
c = 12.5044 (15) Å	µ = 0.08 mm⁻¹
β = 92.990 (2)°	T = 296 K
V = 1440.6 (3) Å³	Block, colourless
Z = 2	0.37 × 0.21 × 0.13 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2847 independent reflections
Radiation source: fine-focus sealed tube	1948 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.973, T_max = 0.990	k = −11→11
10978 measured reflections	l = −15→14

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0511P)² + 0.0145P] where P = (F_o² + 2F_c²)/3
2847 reflections	(Δ/σ)_max < 0.001
313 parameters	Δρ_max = 0.13 e Å⁻³
1 restraint	Δρ_min = −0.11 e Å⁻³

Crystal data top

C₂₈H₄₄O₆	V = 1440.6 (3) Å³
M_r = 476.63	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 12.3443 (15) Å	µ = 0.08 mm⁻¹
b = 9.3455 (11) Å	T = 296 K
c = 12.5044 (15) Å	0.37 × 0.21 × 0.13 mm
β = 92.990 (2)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2847 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1948 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.990	R_int = 0.037
10978 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	1 restraint
wR(F²) = 0.107	H-atom parameters constrained
S = 1.10	Δρ_max = 0.13 e Å⁻³
2847 reflections	Δρ_min = −0.11 e Å⁻³
313 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 F > 2 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
C1	0.2722 (3)	−0.1115 (4)	0.7313 (3)	0.0636 (9)
C2	0.1833 (3)	−0.1464 (4)	0.6548 (3)	0.0673 (9)
H2	0.1539	−0.2371	0.6435	0.081*
C3	0.1512 (3)	−0.0294 (3)	0.6040 (2)	0.0580 (8)
H3	0.0966	−0.0252	0.5499	0.070*
C4	0.2157 (2)	0.0963 (3)	0.6464 (2)	0.0500 (7)
C5	0.0993 (3)	0.4327 (4)	0.6196 (3)	0.0668 (9)
C6	0.0638 (3)	0.2810 (4)	0.6295 (3)	0.0721 (10)
H6A	0.0590	0.2349	0.5599	0.087*
H6B	−0.0066	0.2761	0.6603	0.087*
C7	0.1496 (2)	0.2092 (3)	0.7026 (2)	0.0542 (8)
H7	0.1145	0.1645	0.7627	0.065*
C8	0.2212 (3)	0.3329 (3)	0.7451 (2)	0.0542 (8)
H8	0.2980	0.3106	0.7377	0.065*
C9	0.3545 (2)	0.0949 (3)	0.5128 (2)	0.0516 (7)
H9	0.3389	−0.0079	0.5119	0.062*
C10	0.3496 (3)	0.1518 (4)	0.3983 (2)	0.0639 (9)
H10	0.3613	0.2553	0.4040	0.077*
C11	0.4467 (3)	0.0921 (5)	0.3399 (3)	0.0882 (12)
H11A	0.4386	−0.0107	0.3321	0.106*
H11B	0.4466	0.1334	0.2687	0.106*
C12	0.5536 (3)	0.1242 (5)	0.3987 (3)	0.0906 (13)
H12A	0.6118	0.0834	0.3593	0.109*
H12B	0.5641	0.2270	0.4016	0.109*
C13	0.5596 (3)	0.0655 (4)	0.5105 (3)	0.0786 (11)
H13	0.5532	−0.0389	0.5056	0.094*
C14	0.4636 (3)	0.1210 (4)	0.5701 (3)	0.0630 (9)
H14A	0.4642	0.0756	0.6399	0.076*
H14B	0.4726	0.2231	0.5816	0.076*
C15	0.2398 (3)	0.1322 (4)	0.3384 (3)	0.0806 (11)
H15	0.1842	0.1611	0.3872	0.097*
C16	0.2143 (4)	−0.0210 (5)	0.3039 (3)	0.1099 (15)
H16A	0.1450	−0.0238	0.2653	0.165*
H16B	0.2125	−0.0811	0.3660	0.165*
H16C	0.2693	−0.0547	0.2585	0.165*
C17	0.2291 (5)	0.2304 (7)	0.2419 (4)	0.146 (2)
H17A	0.2808	0.2030	0.1910	0.219*
H17B	0.2425	0.3273	0.2642	0.219*
H17C	0.1571	0.2229	0.2094	0.219*
C18	0.6660 (3)	0.0997 (6)	0.5710 (4)	0.1129 (16)
H18A	0.7251	0.0630	0.5322	0.169*
H18B	0.6670	0.0563	0.6406	0.169*
H18C	0.6734	0.2015	0.5785	0.169*
C19	0.2668 (3)	0.4725 (3)	0.9018 (2)	0.0555 (8)
H19	0.2633	0.5571	0.8555	0.067*
C20	0.2145 (3)	0.5078 (4)	1.0059 (2)	0.0703 (10)
H20	0.2177	0.4204	1.0492	0.084*
C21	0.2846 (4)	0.6188 (4)	1.0667 (3)	0.0892 (12)
H21A	0.2800	0.7087	1.0279	0.107*
H21B	0.2555	0.6344	1.1363	0.107*
C22	0.4031 (4)	0.5765 (5)	1.0825 (3)	0.0920 (12)
H22A	0.4432	0.6540	1.1177	0.110*
H22B	0.4092	0.4931	1.1285	0.110*
C23	0.4521 (3)	0.5434 (4)	0.9774 (3)	0.0752 (10)
H23	0.4483	0.6301	0.9332	0.090*
C24	0.3841 (3)	0.4271 (4)	0.9195 (3)	0.0690 (9)
H24A	0.4140	0.4070	0.8509	0.083*
H24B	0.3877	0.3399	0.9616	0.083*
C25	0.0957 (3)	0.5478 (5)	0.9905 (3)	0.0878 (12)
H25	0.0598	0.4668	0.9538	0.105*
C26	0.0741 (4)	0.6783 (6)	0.9189 (4)	0.1279 (18)
H26A	0.1058	0.7616	0.9528	0.192*
H26B	−0.0028	0.6920	0.9077	0.192*
H26C	0.1056	0.6632	0.8512	0.192*
C27	0.0408 (4)	0.5658 (7)	1.0960 (4)	0.136 (2)
H27A	0.0563	0.4842	1.1409	0.204*
H27B	−0.0362	0.5739	1.0822	0.204*
H27C	0.0676	0.6508	1.1315	0.204*
C28	0.5722 (3)	0.4972 (5)	0.9912 (4)	0.1014 (14)
H28A	0.5779	0.4139	1.0361	0.152*
H28B	0.6142	0.5736	1.0237	0.152*
H28C	0.5990	0.4754	0.9224	0.152*
O1	0.29140 (17)	0.0331 (2)	0.72584 (15)	0.0571 (5)
O2	0.3238 (3)	−0.1869 (3)	0.7920 (2)	0.0953 (9)
O3	0.27166 (15)	0.16972 (19)	0.56934 (14)	0.0511 (5)
O4	0.18960 (19)	0.4565 (2)	0.68011 (17)	0.0668 (6)
O5	0.0572 (2)	0.5251 (3)	0.5659 (2)	0.0991 (9)
O6	0.20131 (17)	0.3581 (2)	0.85066 (15)	0.0589 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.097 (3)	0.046 (2)	0.0488 (19)	0.0005 (19)	0.0076 (19)	0.0070 (16)
C2	0.097 (3)	0.0419 (19)	0.064 (2)	−0.0128 (19)	0.0108 (19)	−0.0021 (17)
C3	0.072 (2)	0.0488 (19)	0.0540 (17)	−0.0082 (17)	0.0060 (15)	−0.0059 (16)
C4	0.0595 (18)	0.0457 (17)	0.0455 (16)	−0.0009 (15)	0.0078 (15)	0.0032 (14)
C5	0.071 (2)	0.061 (2)	0.069 (2)	−0.0050 (19)	0.006 (2)	−0.0044 (19)
C6	0.059 (2)	0.053 (2)	0.105 (3)	0.0005 (17)	0.0085 (19)	−0.014 (2)
C7	0.062 (2)	0.0470 (17)	0.0554 (18)	−0.0062 (16)	0.0189 (16)	−0.0048 (15)
C8	0.0646 (19)	0.0480 (18)	0.0511 (17)	0.0001 (15)	0.0126 (14)	−0.0054 (15)
C9	0.067 (2)	0.0361 (15)	0.0534 (17)	0.0045 (15)	0.0177 (15)	0.0029 (14)
C10	0.084 (2)	0.055 (2)	0.0536 (18)	−0.0023 (18)	0.0141 (17)	0.0020 (16)
C11	0.106 (3)	0.094 (3)	0.068 (2)	0.001 (3)	0.036 (2)	−0.006 (2)
C12	0.091 (3)	0.084 (3)	0.100 (3)	−0.003 (2)	0.045 (2)	−0.009 (3)
C13	0.072 (2)	0.050 (2)	0.116 (3)	0.0031 (18)	0.019 (2)	−0.003 (2)
C14	0.067 (2)	0.0487 (19)	0.074 (2)	0.0003 (17)	0.0115 (18)	0.0031 (17)
C15	0.102 (3)	0.085 (3)	0.0549 (19)	0.001 (2)	0.005 (2)	0.010 (2)
C16	0.129 (4)	0.106 (4)	0.094 (3)	−0.033 (3)	0.002 (3)	−0.002 (3)
C17	0.194 (6)	0.141 (5)	0.098 (3)	−0.025 (5)	−0.035 (4)	0.046 (3)
C18	0.065 (3)	0.104 (4)	0.171 (5)	0.004 (3)	0.014 (3)	−0.008 (3)
C19	0.081 (2)	0.0380 (16)	0.0480 (16)	−0.0005 (16)	0.0063 (15)	−0.0009 (14)
C20	0.108 (3)	0.054 (2)	0.0495 (18)	−0.003 (2)	0.0151 (18)	−0.0012 (16)
C21	0.133 (4)	0.071 (3)	0.064 (2)	0.000 (3)	0.015 (2)	−0.018 (2)
C22	0.134 (4)	0.075 (3)	0.065 (2)	−0.011 (3)	−0.012 (2)	−0.002 (2)
C23	0.095 (3)	0.060 (2)	0.069 (2)	0.002 (2)	−0.0137 (19)	0.0050 (19)
C24	0.089 (3)	0.055 (2)	0.062 (2)	0.0030 (19)	−0.0032 (18)	0.0035 (17)
C25	0.106 (3)	0.077 (3)	0.084 (3)	0.002 (2)	0.035 (2)	−0.020 (2)
C26	0.108 (4)	0.135 (5)	0.143 (4)	0.044 (3)	0.026 (3)	0.002 (4)
C27	0.156 (4)	0.141 (5)	0.118 (4)	−0.004 (4)	0.075 (3)	−0.037 (4)
C28	0.100 (3)	0.092 (3)	0.108 (3)	0.003 (3)	−0.027 (3)	0.011 (3)
O1	0.0767 (14)	0.0461 (12)	0.0482 (11)	−0.0025 (11)	0.0015 (10)	0.0051 (10)
O2	0.151 (3)	0.0613 (16)	0.0715 (15)	0.0074 (16)	−0.0174 (16)	0.0165 (14)
O3	0.0643 (13)	0.0393 (11)	0.0510 (11)	0.0043 (9)	0.0154 (10)	0.0052 (9)
O4	0.0872 (17)	0.0554 (13)	0.0571 (13)	−0.0183 (13)	−0.0033 (12)	0.0089 (11)
O5	0.113 (2)	0.0729 (17)	0.108 (2)	−0.0099 (18)	−0.0277 (17)	0.0170 (18)
O6	0.0830 (14)	0.0477 (12)	0.0474 (11)	−0.0045 (11)	0.0164 (10)	−0.0009 (10)

Geometric parameters (Å, º) top

C1—O2	1.195 (4)	C15—H15	0.9800
C1—O1	1.374 (4)	C16—H16A	0.9600
C1—C2	1.455 (5)	C16—H16B	0.9600
C2—C3	1.316 (4)	C16—H16C	0.9600
C2—H2	0.9300	C17—H17A	0.9600
C3—C4	1.500 (4)	C17—H17B	0.9600
C3—H3	0.9300	C17—H17C	0.9600
C4—O3	1.395 (3)	C18—H18A	0.9600
C4—O1	1.454 (3)	C18—H18B	0.9600
C4—C7	1.528 (4)	C18—H18C	0.9600
C5—O5	1.196 (4)	C19—O6	1.467 (3)
C5—O4	1.334 (4)	C19—C24	1.514 (4)
C5—C6	1.491 (5)	C19—C20	1.519 (4)
C6—C7	1.519 (4)	C19—H19	0.9800
C6—H6A	0.9700	C20—C25	1.516 (5)
C6—H6B	0.9700	C20—C21	1.528 (5)
C7—C8	1.533 (4)	C20—H20	0.9800
C7—H7	0.9800	C21—C22	1.517 (6)
C8—O6	1.375 (3)	C21—H21A	0.9700
C8—O4	1.453 (4)	C21—H21B	0.9700
C8—H8	0.9800	C22—C23	1.507 (5)
C9—O3	1.453 (3)	C22—H22A	0.9700
C9—C14	1.512 (4)	C22—H22B	0.9700
C9—C10	1.525 (4)	C23—C24	1.531 (5)
C9—H9	0.9800	C23—C28	1.545 (5)
C10—C15	1.525 (5)	C23—H23	0.9800
C10—C11	1.540 (5)	C24—H24A	0.9700
C10—H10	0.9800	C24—H24B	0.9700
C11—C12	1.507 (5)	C25—C27	1.524 (5)
C11—H11A	0.9700	C25—C26	1.528 (6)
C11—H11B	0.9700	C25—H25	0.9800
C12—C13	1.500 (5)	C26—H26A	0.9600
C12—H12A	0.9700	C26—H26B	0.9600
C12—H12B	0.9700	C26—H26C	0.9600
C13—C18	1.516 (5)	C27—H27A	0.9600
C13—C14	1.524 (5)	C27—H27B	0.9600
C13—H13	0.9800	C27—H27C	0.9600
C14—H14A	0.9700	C28—H28A	0.9600
C14—H14B	0.9700	C28—H28B	0.9600
C15—C17	1.516 (5)	C28—H28C	0.9600
C15—C16	1.524 (6)

O2—C1—O1	121.6 (3)	H16A—C16—H16B	109.5
O2—C1—C2	130.1 (3)	C15—C16—H16C	109.5
O1—C1—C2	108.3 (3)	H16A—C16—H16C	109.5
C3—C2—C1	109.2 (3)	H16B—C16—H16C	109.5
C3—C2—H2	125.4	C15—C17—H17A	109.5
C1—C2—H2	125.4	C15—C17—H17B	109.5
C2—C3—C4	109.8 (3)	H17A—C17—H17B	109.5
C2—C3—H3	125.1	C15—C17—H17C	109.5
C4—C3—H3	125.1	H17A—C17—H17C	109.5
O3—C4—O1	110.4 (2)	H17B—C17—H17C	109.5
O3—C4—C3	114.5 (2)	C13—C18—H18A	109.5
O1—C4—C3	103.5 (2)	C13—C18—H18B	109.5
O3—C4—C7	105.9 (2)	H18A—C18—H18B	109.5
O1—C4—C7	107.8 (2)	C13—C18—H18C	109.5
C3—C4—C7	114.7 (2)	H18A—C18—H18C	109.5
O5—C5—O4	121.6 (3)	H18B—C18—H18C	109.5
O5—C5—C6	127.8 (4)	O6—C19—C24	111.1 (2)
O4—C5—C6	110.6 (3)	O6—C19—C20	106.4 (2)
C5—C6—C7	105.8 (3)	C24—C19—C20	112.4 (3)
C5—C6—H6A	110.6	O6—C19—H19	108.9
C7—C6—H6A	110.6	C24—C19—H19	108.9
C5—C6—H6B	110.6	C20—C19—H19	108.9
C7—C6—H6B	110.6	C19—C20—C25	113.3 (3)
H6A—C6—H6B	108.7	C19—C20—C21	108.6 (3)
C6—C7—C4	113.6 (3)	C25—C20—C21	114.5 (3)
C6—C7—C8	104.3 (3)	C19—C20—H20	106.6
C4—C7—C8	111.7 (2)	C25—C20—H20	106.6
C6—C7—H7	109.0	C21—C20—H20	106.6
C4—C7—H7	109.0	C22—C21—C20	113.9 (3)
C8—C7—H7	109.0	C22—C21—H21A	108.8
O6—C8—O4	110.2 (2)	C20—C21—H21A	108.8
O6—C8—C7	109.5 (2)	C22—C21—H21B	108.8
O4—C8—C7	105.8 (2)	C20—C21—H21B	108.8
O6—C8—H8	110.4	H21A—C21—H21B	107.7
O4—C8—H8	110.4	C23—C22—C21	111.6 (3)
C7—C8—H8	110.4	C23—C22—H22A	109.3
O3—C9—C14	108.9 (2)	C21—C22—H22A	109.3
O3—C9—C10	107.1 (2)	C23—C22—H22B	109.3
C14—C9—C10	112.3 (2)	C21—C22—H22B	109.3
O3—C9—H9	109.5	H22A—C22—H22B	108.0
C14—C9—H9	109.5	C22—C23—C24	108.9 (3)
C10—C9—H9	109.5	C22—C23—C28	112.7 (3)
C9—C10—C15	114.2 (3)	C24—C23—C28	110.7 (3)
C9—C10—C11	109.0 (3)	C22—C23—H23	108.1
C15—C10—C11	114.6 (3)	C24—C23—H23	108.1
C9—C10—H10	106.1	C28—C23—H23	108.1
C15—C10—H10	106.1	C19—C24—C23	111.5 (3)
C11—C10—H10	106.1	C19—C24—H24A	109.3
C12—C11—C10	112.3 (3)	C23—C24—H24A	109.3
C12—C11—H11A	109.1	C19—C24—H24B	109.3
C10—C11—H11A	109.1	C23—C24—H24B	109.3
C12—C11—H11B	109.1	H24A—C24—H24B	108.0
C10—C11—H11B	109.1	C20—C25—C27	112.9 (4)
H11A—C11—H11B	107.9	C20—C25—C26	114.2 (4)
C13—C12—C11	112.5 (3)	C27—C25—C26	110.3 (4)
C13—C12—H12A	109.1	C20—C25—H25	106.3
C11—C12—H12A	109.1	C27—C25—H25	106.3
C13—C12—H12B	109.1	C26—C25—H25	106.3
C11—C12—H12B	109.1	C25—C26—H26A	109.5
H12A—C12—H12B	107.8	C25—C26—H26B	109.5
C12—C13—C18	112.8 (4)	H26A—C26—H26B	109.5
C12—C13—C14	109.2 (3)	C25—C26—H26C	109.5
C18—C13—C14	111.1 (3)	H26A—C26—H26C	109.5
C12—C13—H13	107.8	H26B—C26—H26C	109.5
C18—C13—H13	107.8	C25—C27—H27A	109.5
C14—C13—H13	107.8	C25—C27—H27B	109.5
C9—C14—C13	114.1 (3)	H27A—C27—H27B	109.5
C9—C14—H14A	108.7	C25—C27—H27C	109.5
C13—C14—H14A	108.7	H27A—C27—H27C	109.5
C9—C14—H14B	108.7	H27B—C27—H27C	109.5
C13—C14—H14B	108.7	C23—C28—H28A	109.5
H14A—C14—H14B	107.6	C23—C28—H28B	109.5
C17—C15—C10	110.9 (4)	H28A—C28—H28B	109.5
C17—C15—C16	109.6 (4)	C23—C28—H28C	109.5
C10—C15—C16	114.7 (4)	H28A—C28—H28C	109.5
C17—C15—H15	107.1	H28B—C28—H28C	109.5
C10—C15—H15	107.1	C1—O1—C4	109.1 (3)
C16—C15—H15	107.1	C4—O3—C9	119.1 (2)
C15—C16—H16A	109.5	C5—O4—C8	112.1 (3)
C15—C16—H16B	109.5	C8—O6—C19	114.9 (2)

O2—C1—C2—C3	−179.5 (4)	C11—C10—C15—C16	53.3 (4)
O1—C1—C2—C3	1.0 (4)	O6—C19—C20—C25	−55.8 (4)
C1—C2—C3—C4	−1.8 (4)	C24—C19—C20—C25	−177.7 (3)
C2—C3—C4—O3	122.0 (3)	O6—C19—C20—C21	175.7 (3)
C2—C3—C4—O1	1.8 (3)	C24—C19—C20—C21	53.8 (4)
C2—C3—C4—C7	−115.3 (3)	C19—C20—C21—C22	−52.8 (4)
O5—C5—C6—C7	176.8 (4)	C25—C20—C21—C22	179.4 (3)
O4—C5—C6—C7	−2.7 (4)	C20—C21—C22—C23	55.7 (4)
C5—C6—C7—C4	−112.9 (3)	C21—C22—C23—C24	−55.7 (4)
C5—C6—C7—C8	8.9 (3)	C21—C22—C23—C28	−178.9 (3)
O3—C4—C7—C6	63.9 (3)	O6—C19—C24—C23	−177.5 (2)
O1—C4—C7—C6	−177.9 (3)	C20—C19—C24—C23	−58.3 (4)
C3—C4—C7—C6	−63.2 (3)	C22—C23—C24—C19	57.5 (4)
O3—C4—C7—C8	−53.6 (3)	C28—C23—C24—C19	−178.1 (3)
O1—C4—C7—C8	64.5 (3)	C19—C20—C25—C27	173.2 (4)
C3—C4—C7—C8	179.2 (3)	C21—C20—C25—C27	−61.4 (5)
C6—C7—C8—O6	106.9 (3)	C19—C20—C25—C26	−59.7 (4)
C4—C7—C8—O6	−130.0 (3)	C21—C20—C25—C26	65.6 (4)
C6—C7—C8—O4	−11.8 (3)	O2—C1—O1—C4	−179.3 (3)
C4—C7—C8—O4	111.3 (3)	C2—C1—O1—C4	0.2 (3)
O3—C9—C10—C15	−58.6 (3)	O3—C4—O1—C1	−124.2 (3)
C14—C9—C10—C15	−178.1 (3)	C3—C4—O1—C1	−1.2 (3)
O3—C9—C10—C11	171.8 (3)	C7—C4—O1—C1	120.7 (3)
C14—C9—C10—C11	52.3 (4)	O1—C4—O3—C9	54.5 (3)
C9—C10—C11—C12	−54.9 (4)	C3—C4—O3—C9	−61.8 (3)
C15—C10—C11—C12	175.7 (3)	C7—C4—O3—C9	170.9 (2)
C10—C11—C12—C13	58.0 (5)	C14—C9—O3—C4	−93.9 (3)
C11—C12—C13—C18	−178.9 (4)	C10—C9—O3—C4	144.5 (2)
C11—C12—C13—C14	−54.8 (4)	O5—C5—O4—C8	175.2 (3)
O3—C9—C14—C13	−172.0 (3)	C6—C5—O4—C8	−5.3 (4)
C10—C9—C14—C13	−53.5 (4)	O6—C8—O4—C5	−107.3 (3)
C12—C13—C14—C9	53.1 (4)	C7—C8—O4—C5	11.0 (3)
C18—C13—C14—C9	178.2 (3)	O4—C8—O6—C19	−65.3 (3)
C9—C10—C15—C17	161.8 (4)	C7—C8—O6—C19	178.7 (2)
C11—C10—C15—C17	−71.5 (5)	C24—C19—O6—C8	−70.9 (3)
C9—C10—C15—C16	−73.5 (4)	C20—C19—O6—C8	166.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O5ⁱ	0.93	2.37	3.289 (5)	168
C8—H8···O1	0.98	2.60	2.947 (4)	101
C14—H14A···O1	0.97	2.47	3.069 (4)	120
C15—H15···O3	0.98	2.47	2.915 (4)	107
C19—H19···O4	0.98	2.51	2.888 (4)	103
C25—H25···O6	0.98	2.45	2.853 (4)	105
C28—H28A···O2ⁱⁱ	0.96	2.59	3.405 (5)	143

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

Experimental details

Crystal data
Chemical formula	C₂₈H₄₄O₆
M_r	476.63
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	12.3443 (15), 9.3455 (11), 12.5044 (15)
β (°)	92.990 (2)
V (Å³)	1440.6 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.37 × 0.21 × 0.13

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.973, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	10978, 2847, 1948
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.107, 1.10
No. of reflections	2847
No. of parameters	313
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.11

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).