Andirobin from X. moluccensis

Jittaniyom, C.; Sommit, D.; Muangsin, N.; Pudhom, K.

doi:10.1107/S1600536812027705

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages o2550-o2551

https://doi.org/10.1107/S1600536812027705

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Andirobin from X. moluccensis

Chutima Jittaniyom,^a Damrong Sommit,^b Nongnuj Muangsin ^c and Khanitha Pudhom ^d ^*

^aDepartment of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand, ^bDepartment of Chemistry, Faculty of Science, Mahanakorn University of Technology, Bangkok 10530, Thailand, ^cResearch Centre of Bioorganic Chemistry, Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok, 10330, Thailand, and ^dCenter for Petroleum, Petrochemicals, and Advanced Materials, Chulalongkorn University, Bangkok 10330, Thailand
^*Correspondence e-mail: nongnuj.j@chula.ac.th

(Received 16 April 2012; accepted 19 June 2012; online 25 July 2012)

The title compound (systematic name: methyl 2-{(1R,2R)-2-[(1aS,4S,4aS,8aS)-4-(furan-3-yl)-4a-methyl-8-methylene-2-oxooctahydrooxireno[2,3-d]isochromen-7-yl]-2,6,6-trimethyl-5-oxocyclohex-3-en-1-yl}acetate), C₂₇H₃₂O₇, was isolated from X. moluccensis seeds from Thailand. The conformations of the six-membered rings are distorted half-chair, chair and half-chair for the isolated cyclohexane, fused cyclohexane and lactone rings, respectively. In addition, the lactone ring bears in an equatorial orientation an essentially planar furan ring (r.m.s. deviation = 0.004 Å), which forms an angle of 63.87 (13)° with the mean plane defined by the ten atoms of the two fused six-membered rings (r.m.s. deviation = 0.213 Å). The absolute configuration was fixed on the basis of literature data.

Related literature

For general background to limonoids and their activities, see: Alvi et al. (1991 ); Yu et al. (2007 ); Li et al. (2009 ). For related structures, see: Chanin et al. (2010 ); Pudhom et al. (2009 , 2010 ). For the bioactivity of limonoids, see: Koul et al. (2004 ); Endo et al. (2002 ); Nakagawa et al. (2001 ); Ravangpai et al. (2011 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₂₇H₃₂O₇
M_r = 468.53
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.8125 (5) Å
b = 12.5907 (7) Å
c = 21.9393 (11) Å
V = 2434.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.48 × 0.40 × 0.36 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
13719 measured reflections
3132 independent reflections
2725 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.117
S = 1.11
5520 reflections
312 parameters
H-atom parameters constrained
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ; software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812027705/lr2061sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812027705/lr2061Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812027705/lr2061Isup3.cml

checkCIF report

Comment top

Limonoids are triterpene derivatives from a precursor with a 4,4,8-trimethyl-17-furanylsteroid skeleton. Limonoid examination of the Meliaceae family is of growing interest due to a range of biological activities, such as insect antifeedants and growth regulators, antibacterial, antifungal, antimalarial, anticancer, antiviral and anti-inflammatory activities (Koul et al., 2004; Endo et al., 2002; Nakagawa et al., 2001; Ravangpai, et al., 2011). The genus Xylocarpus (Meliaceae) has proved to be a rich source of an array of structurally diverse limonoids, including gedunin, andirobin, mexicanolide and phragmalin type limonoids, with a broad range of biological activities (Alvi et al., 1991; Yu et al., 2007; Li et al., 2009). We have recently reported the isolation and identification a number of limonoids from three Thai mangroves in this genus, X. granatum, X. moluccensis and X. rumphii (Chanin et al., 2010; Pudhom et al., 2009; Pudhom et al., 2010). Herein, we report the complete assignments of NMR and the crystal structure of the title compound isolated from X. moluccensis seeds.

In the molecular structure, the conformation of the six-membered rings are distorted half-chair, chair and half-chair for the isolated cyclohenane, fused cyclohexane and lactone ring respectively (Cremer & Pople, 1975). In addition, the lactone ring bears in equatorial orientation a planar furan ring (r.m.s. deviation= 0.004 Å) which form an angle of 63.87 (13)^owith the mean square plane (r.m.s. deviation Å) defined by the ten atoms of the two fused six-membered rings.

Related literature top

For general background to limonoids and their activities, see: Alvi et al. (1991); Yu et al. (2007); Li et al. (2009). For related structures, see: Chanin et al. (2010); Pudhom et al. (2009, 2010). For the bioactivity of limonoids, see: Koul et al. (2004); Endo et al. (2002); Nakagawa et al. (2001); Ravangpai, et al. (2011). For puckering parameters, see:Cremer & Pople (1975).

Experimental top

General Experiment Procedures. Melting point was measured using a Fisher-Johns melting point apparatus. NMR spectra were recorded with a Bruker AV400 (¹H, 400 MHz; ¹³C, 100 MHz) spectrometer using tetramethylsilane as an internal standard. Mass spectra were obtained from a Bruker micrOTOF mass spectrometer.

Plant Material. Fruits of X. moluccensis were collected from Surat Thani province, Thailand, in January 2010. Plant materials were identified by Royal Forest Department, Bangkok, Thailand.

Extraction and Isolation of Andirobin (1). Air-dried powdered seeds of X. moluccensis (2 kg) were extracted with MeOH (5L x 2, each for two days) at room temperature. Extracts were pooled and the solvent were removed under reduced pressure. The combined MeOH extract was then suspended in water and partitioned with EtOAc. The EtOAc crude extract obtained (30 g) was chromatographed on a sililca gel column eluted with a gradient of acetone-hexane (from 1:9 to 1:0) to yield 12 fractions. Fraction 2 was further purified by silica gel column chromatography eluting with a 1:9 mixture of acetone-hexane and recrystallized from MeOH to afford the title compound (1, 25.0 mg).

Andirobin (1): colorless crystals; ¹H NMR (400 MHz, CDCl₃) d 7.34 (1H, s, H-23), 7.33 (1H, s, H-21), 7.07 (1H, d, J = 10.4 Hz, H-1), 6.27 (1H, s, H-22), 5.99 (1H, d, J = 10.4 Hz, H-2), 5.41 (1H, s, H-17), 5.30 (1H, s, H-30a), 5.20 (1H, s, H-30b), 3.97 (1H, s, H-15), 3.64 (3H, s, 7-COOCH₃), 2.62 (1H, dd, J = 3.2, 6.8 Hz, H-5), 2.44 (1H, dd, J = 7.2, 17.2 Hz, H-6a), 2.39 (1H, d, J = 6.8 Hz, H-9), 2.28 (1H, dd, J = 3.2, 17.2 Hz, H-6 b), 1.90 (1H, m, H-11a), 1.73 (1H, m, H-11b), 1.60 (1H, m, H-12a), 1.16 (1H, m, H-12b), 1.04 (3H, s, 28-CH₃), 1.01 (3H, s, 29-CH₃), 0.90 (3H, s, 19-CH₃), 0.87 (3H, s, 18-CH₃);

¹³C NMR (100 MHz, CDCl₃) d 203.7 (C=O, C-3), 174.3 (C=O, C-7), 166.7 (C=O, C-16), 153.5 (CH, C-1), 143.2 (CH, C-23), 140.9 (CH, C-21), 138.9 (C, C-8), 125.7 (CH, C-2), 122.3 (CH₂, C-30), 119.8 (C, C-20), 109.7 (CH, C-22), 77.4 (CH, C-15), 67.8 (C, C-14), 55.5 (CH, C-17), 52.1 (CH₃, 7-COOCH₃), 48.8 (CH, C-9), 46.1 (C, C-4), 43.1 (C, C-10), 42.8 (CH, C-5), 38.6 (C, C-13), 31.5 (CH₂, C-6), 29.5 (CH₂, C-12), 22.7 (CH₃, C-29), 22.5 (CH₃, C-28), 21.3 (CH₂, C-11), 20.2 (CH₃, C-19), 14.6 (CH₃, C-18).

Structure description top

For general background to limonoids and their activities, see: Alvi et al. (1991); Yu et al. (2007); Li et al. (2009). For related structures, see: Chanin et al. (2010); Pudhom et al. (2009, 2010). For the bioactivity of limonoids, see: Koul et al. (2004); Endo et al. (2002); Nakagawa et al. (2001); Ravangpai, et al. (2011). For puckering parameters, see:Cremer & Pople (1975).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997; software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

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

methyl 2-{(1R,2R)-2-[(1aS,4S,4aS,8aS)- 4-(furan-3-yl)-4a-methyl-8-methylene-2- oxooctahydrooxireno[2,3-d]isochromen-7-yl]-2,6,6-trimethyl- 5-oxocyclohex-3-en-1-yl}acetate top

Crystal data top

C₂₇H₃₂O₇	Z = 4
M_r = 468.53	F(000) = 1000
Orthorhombic, P2₁2₁2₁	D_x = 1.278 Mg m⁻³
Hall symbol: P 2ac 2ab	Mo Kα radiation, λ = 0.71073 Å
a = 8.8125 (5) Å	µ = 0.09 mm⁻¹
b = 12.5907 (7) Å	T = 296 K
c = 21.9393 (11) Å	Prism, colourless
V = 2434.3 (2) Å³	0.48 × 0.40 × 0.36 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2725 reflections with I > 2σ(I)
Radiation source: Mo Kα	R_int = 0.020
Graphite monochromator	θ_max = 27.5°, θ_min = 1.9°
φ and ω scans	h = −11→7
13719 measured reflections	k = −15→15
3132 independent reflections	l = −28→19

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.041	w = 1/[σ²(F_o²) + (0.0714P)² + 0.1995P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.117	(Δ/σ)_max = 0.014
S = 1.11	Δρ_max = 0.68 e Å⁻³
5520 reflections	Δρ_min = −0.18 e Å⁻³
312 parameters

Crystal data top

C₂₇H₃₂O₇	V = 2434.3 (2) Å³
M_r = 468.53	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.8125 (5) Å	µ = 0.09 mm⁻¹
b = 12.5907 (7) Å	T = 296 K
c = 21.9393 (11) Å	0.48 × 0.40 × 0.36 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2725 reflections with I > 2σ(I)
13719 measured reflections	R_int = 0.020
3132 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.11	Δρ_max = 0.68 e Å⁻³
5520 reflections	Δρ_min = −0.18 e Å⁻³
312 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.8749 (3)	0.19440 (18)	0.08892 (10)	0.0410 (5)
H1	0.7868	0.1870	0.0660	0.049*
C2	0.9926 (3)	0.2397 (2)	0.06213 (12)	0.0504 (6)
H2	0.9842	0.2570	0.0211	0.060*
C3	1.1348 (3)	0.2640 (2)	0.09316 (12)	0.0487 (6)
C4	1.1303 (3)	0.25998 (19)	0.16248 (12)	0.0427 (5)
C5	1.0339 (2)	0.16189 (17)	0.18228 (10)	0.0344 (4)
H5	1.0890	0.1003	0.1664	0.041*
C6	1.0335 (3)	0.1469 (2)	0.25150 (11)	0.0417 (5)
H6A	1.0424	0.2159	0.2708	0.050*
H6B	0.9369	0.1166	0.2636	0.050*
C7	1.1586 (3)	0.07683 (19)	0.27427 (10)	0.0406 (5)
C8	0.6587 (2)	0.00557 (17)	0.15184 (10)	0.0352 (4)
C9	0.8277 (2)	0.03182 (16)	0.15559 (9)	0.0324 (4)
H9	0.8598	0.0073	0.1960	0.039*
C10	0.8716 (2)	0.15387 (17)	0.15342 (10)	0.0338 (4)
C11	0.9130 (2)	−0.04026 (19)	0.10972 (10)	0.0377 (5)
H11A	1.0170	−0.0156	0.1068	0.045*
H11B	0.9156	−0.1118	0.1261	0.045*
C12	0.8468 (2)	−0.04512 (19)	0.04580 (10)	0.0364 (4)
H12A	0.9024	−0.0975	0.0223	0.044*
H12B	0.8606	0.0233	0.0262	0.044*
C13	0.6761 (2)	−0.07398 (16)	0.04482 (9)	0.0321 (4)
C14	0.5934 (2)	−0.00153 (17)	0.08910 (10)	0.0338 (4)
C15	0.4320 (2)	0.0194 (2)	0.07674 (11)	0.0436 (5)
H15	0.3670	0.0315	0.1123	0.052*
C16	0.3595 (3)	−0.0313 (2)	0.02300 (11)	0.0466 (6)
C17	0.6142 (2)	−0.05036 (19)	−0.01938 (10)	0.0369 (5)
H17	0.6351	0.0243	−0.0288	0.044*
C18	0.6499 (3)	−0.18975 (18)	0.06402 (11)	0.0447 (5)
H18A	0.5447	−0.2074	0.0588	0.067*
H18B	0.6776	−0.1984	0.1060	0.067*
H18C	0.7109	−0.2358	0.0392	0.067*
C19	0.7500 (3)	0.21722 (19)	0.18871 (12)	0.0447 (6)
H19A	0.7865	0.2878	0.1964	0.067*
H19B	0.7291	0.1825	0.2267	0.067*
H19C	0.6587	0.2208	0.1649	0.067*
C20	0.6791 (3)	−0.11713 (19)	−0.06933 (10)	0.0394 (5)
C21	0.7912 (3)	−0.0869 (2)	−0.10764 (12)	0.0569 (7)
H21	0.8380	−0.0207	−0.1070	0.068*
C22	0.6448 (4)	−0.2222 (2)	−0.08653 (13)	0.0603 (7)
H22	0.5727	−0.2659	−0.0684	0.072*
C23	0.7334 (4)	−0.2479 (3)	−0.13315 (12)	0.0614 (8)
H23	0.7318	−0.3129	−0.1533	0.074*
C28	1.0646 (3)	0.3679 (2)	0.18309 (17)	0.0640 (8)
H28A	1.0457	0.3662	0.2262	0.096*
H28B	0.9713	0.3813	0.1618	0.096*
H28C	1.1360	0.4233	0.1741	0.096*
C29	1.2920 (3)	0.2503 (2)	0.18786 (14)	0.0534 (6)
H29A	1.3322	0.1816	0.1780	0.080*
H29B	1.2898	0.2590	0.2313	0.080*
H29C	1.3549	0.3043	0.1701	0.080*
C30	0.5775 (3)	−0.0189 (2)	0.20065 (11)	0.0503 (6)
H30A	0.4774	−0.0411	0.1963	0.060*
H30B	0.6205	−0.0139	0.2392	0.060*
C31	1.3128 (4)	0.0371 (3)	0.35953 (15)	0.0744 (9)
H31A	1.2729	−0.0330	0.3658	0.112*
H31B	1.3411	0.0674	0.3980	0.112*
H31C	1.4004	0.0333	0.3336	0.112*
O1	0.8261 (3)	−0.1661 (2)	−0.14718 (10)	0.0712 (6)
O2	0.44932 (17)	−0.06685 (16)	−0.02238 (8)	0.0484 (4)
O3	0.54407 (18)	0.09958 (13)	0.06392 (8)	0.0427 (4)
O4	0.22495 (19)	−0.0432 (2)	0.01901 (10)	0.0681 (6)
O5	1.2467 (2)	0.2941 (2)	0.06570 (11)	0.0795 (7)
O6	1.2129 (2)	0.00409 (15)	0.24700 (8)	0.0535 (4)
O7	1.1985 (2)	0.10284 (18)	0.33109 (8)	0.0591 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0448 (12)	0.0358 (11)	0.0423 (12)	0.0015 (10)	−0.0057 (10)	0.0053 (9)
C2	0.0575 (14)	0.0491 (14)	0.0446 (13)	−0.0022 (12)	0.0010 (11)	0.0135 (11)
C3	0.0472 (13)	0.0420 (12)	0.0571 (15)	−0.0019 (11)	0.0068 (12)	0.0113 (11)
C4	0.0369 (10)	0.0364 (11)	0.0549 (14)	−0.0032 (9)	0.0027 (10)	−0.0047 (10)
C5	0.0313 (9)	0.0342 (10)	0.0377 (11)	0.0007 (9)	0.0029 (9)	−0.0039 (9)
C6	0.0383 (11)	0.0486 (13)	0.0380 (11)	0.0017 (10)	0.0011 (10)	−0.0083 (10)
C7	0.0340 (10)	0.0505 (13)	0.0373 (11)	−0.0068 (10)	0.0002 (9)	−0.0020 (10)
C8	0.0333 (9)	0.0357 (10)	0.0368 (10)	0.0013 (9)	0.0054 (9)	−0.0015 (9)
C9	0.0317 (9)	0.0339 (10)	0.0316 (9)	0.0027 (8)	0.0000 (8)	0.0026 (8)
C10	0.0317 (9)	0.0330 (10)	0.0368 (10)	0.0028 (8)	0.0011 (9)	−0.0006 (8)
C11	0.0320 (9)	0.0398 (11)	0.0414 (11)	0.0074 (9)	−0.0018 (9)	−0.0077 (10)
C12	0.0293 (9)	0.0411 (11)	0.0386 (10)	0.0025 (9)	0.0041 (9)	−0.0052 (9)
C13	0.0306 (9)	0.0333 (10)	0.0325 (10)	−0.0015 (8)	0.0019 (8)	0.0001 (8)
C14	0.0295 (9)	0.0351 (10)	0.0367 (10)	0.0001 (8)	0.0056 (8)	0.0020 (9)
C15	0.0309 (10)	0.0559 (14)	0.0438 (12)	0.0045 (10)	0.0045 (9)	−0.0038 (11)
C16	0.0320 (10)	0.0609 (15)	0.0470 (13)	0.0008 (11)	0.0005 (10)	0.0015 (11)
C17	0.0299 (9)	0.0444 (11)	0.0365 (10)	−0.0002 (9)	0.0006 (8)	0.0017 (10)
C18	0.0554 (13)	0.0355 (11)	0.0433 (12)	−0.0041 (11)	0.0017 (11)	0.0028 (9)
C19	0.0380 (11)	0.0396 (12)	0.0565 (14)	0.0083 (10)	0.0023 (11)	−0.0089 (11)
C20	0.0365 (10)	0.0490 (12)	0.0327 (10)	−0.0007 (10)	−0.0034 (9)	0.0000 (10)
C21	0.0575 (15)	0.0646 (16)	0.0486 (14)	−0.0055 (14)	0.0143 (13)	−0.0092 (13)
C22	0.0700 (18)	0.0625 (16)	0.0485 (14)	−0.0169 (15)	0.0043 (14)	−0.0103 (13)
C23	0.079 (2)	0.0610 (17)	0.0440 (14)	0.0081 (16)	−0.0053 (14)	−0.0161 (13)
C28	0.0568 (16)	0.0386 (13)	0.097 (2)	−0.0021 (12)	0.0090 (16)	−0.0122 (14)
C29	0.0393 (11)	0.0538 (15)	0.0671 (16)	−0.0080 (12)	−0.0017 (12)	−0.0075 (13)
C30	0.0443 (12)	0.0640 (16)	0.0426 (12)	−0.0058 (12)	0.0092 (11)	0.0043 (12)
C31	0.0599 (16)	0.102 (3)	0.0610 (17)	0.0075 (19)	−0.0247 (15)	−0.0005 (18)
O1	0.0636 (12)	0.0953 (17)	0.0548 (11)	0.0116 (13)	0.0136 (10)	−0.0144 (11)
O2	0.0303 (7)	0.0707 (12)	0.0441 (9)	−0.0009 (8)	−0.0025 (7)	−0.0084 (8)
O3	0.0379 (7)	0.0408 (8)	0.0493 (9)	0.0077 (7)	−0.0028 (7)	0.0008 (7)
O4	0.0308 (8)	0.1065 (17)	0.0671 (12)	−0.0061 (10)	0.0017 (9)	−0.0101 (13)
O5	0.0559 (12)	0.110 (2)	0.0727 (13)	−0.0154 (12)	0.0136 (11)	0.0291 (14)
O6	0.0519 (10)	0.0581 (11)	0.0504 (10)	0.0105 (9)	−0.0017 (8)	−0.0012 (9)
O7	0.0537 (10)	0.0788 (13)	0.0450 (10)	0.0036 (10)	−0.0149 (8)	−0.0079 (9)

Geometric parameters (Å, º) top

C1—C2	1.321 (3)	C14—C15	1.471 (3)
C1—C10	1.505 (3)	C15—O3	1.440 (3)
C1—H1	0.9300	C15—C16	1.485 (3)
C2—C3	1.459 (4)	C15—H15	0.9800
C2—H2	0.9300	C16—O4	1.198 (3)
C3—O5	1.215 (3)	C16—O2	1.348 (3)
C3—C4	1.522 (4)	C17—O2	1.469 (2)
C4—C29	1.534 (3)	C17—C20	1.495 (3)
C4—C28	1.545 (3)	C17—H17	0.9800
C4—C5	1.561 (3)	C18—H18A	0.9600
C5—C6	1.530 (3)	C18—H18B	0.9600
C5—C10	1.567 (3)	C18—H18C	0.9600
C5—H5	0.9800	C19—H19A	0.9600
C6—C7	1.498 (3)	C19—H19B	0.9600
C6—H6A	0.9700	C19—H19C	0.9600
C6—H6B	0.9700	C20—C21	1.351 (4)
C7—O6	1.194 (3)	C20—C22	1.408 (4)
C7—O7	1.336 (3)	C21—O1	1.358 (3)
C8—C30	1.324 (3)	C21—H21	0.9300
C8—C14	1.495 (3)	C22—C23	1.327 (4)
C8—C9	1.528 (3)	C22—H22	0.9300
C9—C11	1.550 (3)	C23—O1	1.350 (4)
C9—C10	1.585 (3)	C23—H23	0.9300
C9—H9	0.9800	C28—H28A	0.9600
C10—C19	1.545 (3)	C28—H28B	0.9600
C11—C12	1.520 (3)	C28—H28C	0.9600
C11—H11A	0.9700	C29—H29A	0.9600
C11—H11B	0.9700	C29—H29B	0.9600
C12—C13	1.547 (3)	C29—H29C	0.9600
C12—H12A	0.9700	C30—H30A	0.9300
C12—H12B	0.9700	C30—H30B	0.9300
C13—C14	1.519 (3)	C31—O7	1.445 (4)
C13—C18	1.535 (3)	C31—H31A	0.9600
C13—C17	1.540 (3)	C31—H31B	0.9600
C14—O3	1.454 (3)	C31—H31C	0.9600

C2—C1—C10	125.4 (2)	C15—C14—C13	116.97 (19)
C2—C1—H1	117.3	C8—C14—C13	116.10 (17)
C10—C1—H1	117.3	O3—C15—C14	59.93 (13)
C1—C2—C3	123.9 (2)	O3—C15—C16	116.2 (2)
C1—C2—H2	118.1	C14—C15—C16	119.0 (2)
C3—C2—H2	118.1	O3—C15—H15	116.5
O5—C3—C2	122.1 (2)	C14—C15—H15	116.5
O5—C3—C4	121.8 (3)	C16—C15—H15	116.5
C2—C3—C4	115.9 (2)	O4—C16—O2	119.0 (2)
C3—C4—C29	109.9 (2)	O4—C16—C15	122.5 (2)
C3—C4—C28	105.8 (2)	O2—C16—C15	118.41 (18)
C29—C4—C28	108.2 (2)	O2—C17—C20	105.46 (18)
C3—C4—C5	108.59 (19)	O2—C17—C13	111.37 (17)
C29—C4—C5	110.0 (2)	C20—C17—C13	115.22 (18)
C28—C4—C5	114.23 (19)	O2—C17—H17	108.2
C6—C5—C4	112.02 (19)	C20—C17—H17	108.2
C6—C5—C10	113.03 (17)	C13—C17—H17	108.2
C4—C5—C10	115.81 (18)	C13—C18—H18A	109.5
C6—C5—H5	104.9	C13—C18—H18B	109.5
C4—C5—H5	104.9	H18A—C18—H18B	109.5
C10—C5—H5	104.9	C13—C18—H18C	109.5
C7—C6—C5	113.70 (19)	H18A—C18—H18C	109.5
C7—C6—H6A	108.8	H18B—C18—H18C	109.5
C5—C6—H6A	108.8	C10—C19—H19A	109.5
C7—C6—H6B	108.8	C10—C19—H19B	109.5
C5—C6—H6B	108.8	H19A—C19—H19B	109.5
H6A—C6—H6B	107.7	C10—C19—H19C	109.5
O6—C7—O7	123.4 (2)	H19A—C19—H19C	109.5
O6—C7—C6	125.4 (2)	H19B—C19—H19C	109.5
O7—C7—C6	111.1 (2)	C21—C20—C22	104.8 (2)
C30—C8—C14	121.5 (2)	C21—C20—C17	125.2 (2)
C30—C8—C9	122.2 (2)	C22—C20—C17	130.0 (2)
C14—C8—C9	115.96 (17)	C20—C21—O1	110.9 (3)
C8—C9—C11	108.14 (17)	C20—C21—H21	124.6
C8—C9—C10	116.50 (17)	O1—C21—H21	124.6
C11—C9—C10	115.45 (17)	C23—C22—C20	108.0 (3)
C8—C9—H9	105.2	C23—C22—H22	126.0
C11—C9—H9	105.2	C20—C22—H22	126.0
C10—C9—H9	105.2	C22—C23—O1	110.2 (3)
C1—C10—C19	108.03 (19)	C22—C23—H23	124.9
C1—C10—C5	109.93 (18)	O1—C23—H23	124.9
C19—C10—C5	113.42 (18)	C4—C28—H28A	109.5
C1—C10—C9	111.20 (17)	C4—C28—H28B	109.5
C19—C10—C9	108.42 (17)	H28A—C28—H28B	109.5
C5—C10—C9	105.86 (16)	C4—C28—H28C	109.5
C12—C11—C9	115.89 (17)	H28A—C28—H28C	109.5
C12—C11—H11A	108.3	H28B—C28—H28C	109.5
C9—C11—H11A	108.3	C4—C29—H29A	109.5
C12—C11—H11B	108.3	C4—C29—H29B	109.5
C9—C11—H11B	108.3	H29A—C29—H29B	109.5
H11A—C11—H11B	107.4	C4—C29—H29C	109.5
C11—C12—C13	113.28 (18)	H29A—C29—H29C	109.5
C11—C12—H12A	108.9	H29B—C29—H29C	109.5
C13—C12—H12A	108.9	C8—C30—H30A	120.0
C11—C12—H12B	108.9	C8—C30—H30B	120.0
C13—C12—H12B	108.9	H30A—C30—H30B	120.0
H12A—C12—H12B	107.7	O7—C31—H31A	109.5
C14—C13—C18	108.80 (18)	O7—C31—H31B	109.5
C14—C13—C17	107.38 (17)	H31A—C31—H31B	109.5
C18—C13—C17	112.39 (18)	O7—C31—H31C	109.5
C14—C13—C12	108.47 (17)	H31A—C31—H31C	109.5
C18—C13—C12	111.46 (19)	H31B—C31—H31C	109.5
C17—C13—C12	108.19 (17)	C23—O1—C21	106.1 (2)
O3—C14—C15	58.98 (15)	C16—O2—C17	120.06 (18)
O3—C14—C8	114.37 (18)	C15—O3—C14	61.09 (14)
C15—C14—C8	122.08 (19)	C7—O7—C31	116.5 (2)
O3—C14—C13	115.22 (17)

C10—C1—C2—C3	−4.6 (4)	C9—C8—C14—C15	−153.4 (2)
C1—C2—C3—O5	171.1 (3)	C30—C8—C14—C13	−122.1 (2)
C1—C2—C3—C4	−14.6 (4)	C9—C8—C14—C13	52.1 (3)
O5—C3—C4—C29	−24.3 (4)	C18—C13—C14—O3	−151.59 (18)
C2—C3—C4—C29	161.4 (2)	C17—C13—C14—O3	−29.7 (2)
O5—C3—C4—C28	92.2 (3)	C12—C13—C14—O3	87.0 (2)
C2—C3—C4—C28	−82.1 (3)	C18—C13—C14—C15	−85.1 (2)
O5—C3—C4—C5	−144.7 (3)	C17—C13—C14—C15	36.8 (3)
C2—C3—C4—C5	41.0 (3)	C12—C13—C14—C15	153.5 (2)
C3—C4—C5—C6	175.64 (19)	C18—C13—C14—C8	70.8 (2)
C29—C4—C5—C6	55.3 (3)	C17—C13—C14—C8	−167.32 (18)
C28—C4—C5—C6	−66.5 (3)	C12—C13—C14—C8	−50.6 (2)
C3—C4—C5—C10	−52.7 (2)	C8—C14—C15—O3	101.0 (2)
C29—C4—C5—C10	−173.07 (19)	C13—C14—C15—O3	−104.6 (2)
C28—C4—C5—C10	65.1 (3)	O3—C14—C15—C16	105.2 (2)
C4—C5—C6—C7	−90.5 (2)	C8—C14—C15—C16	−153.8 (2)
C10—C5—C6—C7	136.50 (19)	C13—C14—C15—C16	0.6 (3)
C5—C6—C7—O6	−31.4 (3)	O3—C15—C16—O4	−132.8 (3)
C5—C6—C7—O7	151.5 (2)	C14—C15—C16—O4	158.6 (3)
C30—C8—C9—C11	127.1 (2)	O3—C15—C16—O2	48.4 (3)
C14—C8—C9—C11	−47.0 (2)	C14—C15—C16—O2	−20.2 (4)
C30—C8—C9—C10	−100.9 (3)	C14—C13—C17—O2	−58.0 (2)
C14—C8—C9—C10	84.9 (2)	C18—C13—C17—O2	61.6 (2)
C2—C1—C10—C19	118.2 (3)	C12—C13—C17—O2	−174.94 (18)
C2—C1—C10—C5	−6.1 (3)	C14—C13—C17—C20	−178.09 (18)
C2—C1—C10—C9	−123.0 (3)	C18—C13—C17—C20	−58.5 (3)
C6—C5—C10—C1	166.66 (19)	C12—C13—C17—C20	65.0 (2)
C4—C5—C10—C1	35.5 (2)	O2—C17—C20—C21	137.5 (3)
C6—C5—C10—C19	45.6 (3)	C13—C17—C20—C21	−99.2 (3)
C4—C5—C10—C19	−85.6 (2)	O2—C17—C20—C22	−44.4 (3)
C6—C5—C10—C9	−73.1 (2)	C13—C17—C20—C22	78.9 (3)
C4—C5—C10—C9	155.70 (18)	C22—C20—C21—O1	0.5 (3)
C8—C9—C10—C1	−81.7 (2)	C17—C20—C21—O1	179.0 (2)
C11—C9—C10—C1	46.8 (2)	C21—C20—C22—C23	−0.9 (3)
C8—C9—C10—C19	36.9 (3)	C17—C20—C22—C23	−179.3 (3)
C11—C9—C10—C19	165.38 (18)	C20—C22—C23—O1	0.9 (4)
C8—C9—C10—C5	158.90 (17)	C22—C23—O1—C21	−0.6 (4)
C11—C9—C10—C5	−72.6 (2)	C20—C21—O1—C23	0.0 (3)
C8—C9—C11—C12	48.3 (3)	O4—C16—O2—C17	178.2 (3)
C10—C9—C11—C12	−84.2 (2)	C15—C16—O2—C17	−3.0 (4)
C9—C11—C12—C13	−53.0 (3)	C20—C17—O2—C16	169.0 (2)
C11—C12—C13—C14	50.4 (2)	C13—C17—O2—C16	43.4 (3)
C11—C12—C13—C18	−69.3 (2)	C16—C15—O3—C14	−109.9 (2)
C11—C12—C13—C17	166.60 (19)	C8—C14—O3—C15	−114.1 (2)
C30—C8—C14—O3	99.9 (3)	C13—C14—O3—C15	107.6 (2)
C9—C8—C14—O3	−85.9 (2)	O6—C7—O7—C31	−0.4 (4)
C30—C8—C14—C15	32.5 (3)	C6—C7—O7—C31	176.7 (2)

Experimental details

Crystal data
Chemical formula	C₂₇H₃₂O₇
M_r	468.53
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	8.8125 (5), 12.5907 (7), 21.9393 (11)
V (Å³)	2434.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.48 × 0.40 × 0.36

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	13719, 3132, 2725
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.117, 1.11
No. of reflections	5520
No. of parameters	312
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.68, −0.18

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997, publCIF (Westrip, 2010).

Acknowledgements

Financial support from the 90^th Anniversary of Chulalongkorn University Fund (Ratchadaphisek Somphot Endowment Fund) and the Higher Education Research Promotion and National Research University Project of Thailand, Office of the Higher Education Commission (AS613A), is gratefully acknowledged. The authors are also grateful for research funding from the Thai Government Stimulus Package 2 (TKK2555), under the Project for Establishment of a Comprehensive Center for Innovative Food, Health Products and Agriculture.

References

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