E-Notopterol

Schinkovitz, A.; Belaj, F.; Kunert, O.; Bauer, R.

doi:10.1107/S1600536809005030

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o545

doi:10.1107/S1600536809005030

Open

access

E-Notopterol

Andreas Schinkovitz,^a Ferdinand Belaj,^b ^* Olaf Kunert ^c and Rudolf Bauer ^a

^aInstitute of Pharmaceutical Sciences, Department of Pharmacognosy, Karl-Franzens University Graz, Universitätsplatz 4, A-8010 Graz, Austria, ^bInstitute of Chemistry, Karl-Franzens University Graz, Schubertstrasse 1, A-8010 Graz, Austria, and ^cInstitute of Pharmaceutical Sciences, Department of Pharmaceutical Chemistry, Karl-Franzens University Graz, Universitätsplatz 1, A-8010 Graz, Austria
^*Correspondence e-mail: ferdinand.belaj@uni-graz.at

(Received 11 February 2009; accepted 11 February 2009; online 18 February 2009)

The title compound (systematic name: 4-{[(2E)-5-hydroxy-3,7-dimethylocta-2,6-dien-1-yl]oxy}-7H-furo[3,2-g][1]benzopyran-7-one), C₂₁H₂₂O₅, is a known furanocoumarin, which was isolated from the Chinese herbal product Radix seu Rhizoma Notopterygii. The crystal structure shows a weak O—H⋯O hydrogen bond.

Related literature

For the isolation, see: Yang et al. (1994 ); Xiao et al. (1994 ). For NMR shifts and coupling constants of related compounds, see: Hasegawa et al. (1999 ); Chemical Abstract Service (2009 ).

Experimental

Crystal data

C₂₁H₂₂O₅
M_r = 354.39
Triclinic, $[P \overline 1]$
a = 6.4317 (10) Å
b = 8.0912 (16) Å
c = 17.206 (3) Å
α = 91.802 (15)°
β = 94.240 (13)°
γ = 97.473 (15)°
V = 884.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 95 K
0.48 × 0.44 × 0.32 mm

Data collection

Stoe four-circle diffractometer
Absorption correction: none
4234 measured reflections
3462 independent reflections
2941 reflections with I > 2σ(I)
R_int = 0.023
3 standard reflections every 100 reflections intensity decay: 0.4%

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.113
S = 1.04
3462 reflections
249 parameters
Only H-atom displacement parameters refined
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H51⋯O8ⁱ	0.84	2.57	3.2193 (16)	135
Symmetry code: (i) -x+1, -y+2, -z+1.

Data collection: local software; cell refinement: local software; data reduction: local software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: modified ORTEP (Johnson, 1965 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809005030/bt2871sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809005030/bt2871Isup2.hkl

checkCIF report

Comment top

Rhizoma seu Radix Notopterygii is a herbal preparation commonly used in traditional Chinese medicine. It may either contain roots or rhizomes of N. incisum or N. forbesii (Apiaceae) or a mixture of both plants. The isolation of E-Notopterol (Fig.1) has been previously reported for both species (Yang et al., 1994; Xiao et al. 1994), which naturally occur in the region of South Central Asia, but the crystal structure has not been reported until now. In the process of structure elucidation, the title compound was primarily identified by ¹H and ¹³C NMR experiments. Observed chemical shifts and coupling constants were in compliance with previously published literature (Hasegawa et al., 1999; Chemical Abstract Service, 2009). Further support was provided by the ESI-MS analysis, indicating the pseudo molecular ion at 377.29 m/z [M—Na⁺].

The crystal structure analysis confirmed the proposed structure as 4-{[(2E)-5-hydroxy-3,7-dimethyl- octa-2,6-dien-1-yl]oxy}-7H-furo[3,2-g][1]benzopyran-7-one. All the atoms are lying on general positions. In Fig. 1 the S-enantiomer of the racemate is shown. The least-squares plane through the non-H atoms around the double bond C42=C43 enclose an angle of 12.36 (9)° with the plane through the atoms around C46=C47, and further an angle of 41.35 (6)° with the plane through the tricycle. The packing is dominated by an antiparallel stacking of the tricycles (s. Fig. 2) preventing the formation of a strong hydrogen bond of the OH group [O5—H51···.O8ⁱ 134.5°, O5···.O8ⁱ 3.2193 (16) Å; symmetry transformation used to generate the equivalent atom: (i) 1 - x, 2 - y, 1 - z].

Related literature top

For the isolation, see: Yang et al. (1994); Xiao et al. (1994). For NMR shifts and coupling constants of related compounds, see: Hasegawa et al. (1999); Chemical Abstract Service (2009).

Experimental top

Plant Material: Rhizoma seu Radix Notopterygii was purchased from Plantasia (Oberndorf, Austria).

Isolation and purification: Plant material (2000 g) was grinded and extracted with 11 L dichloromethane at room temperature, yielding 381.87 g of dried extract after vacuum evaporation. Next 100 g dried extract were fractionated on a Silicagel 60 column (230–400 mesh, Merck, Darmstadt, Germany; size: 8.5 x 20 cm). In the process a stepwise gradient elution starting from 100% hexane (Hex) and going to 100% ethylacetate (EtOAc) was performed. For each step (2400 ml) the content of Hex in the eluent was reduced by 16.7 vol.%, and 6–8 subfractions were collected. Subfraction D7 collected between 2030 ml and 2400 ml from eluent D (Hex:EtOAc: 50:50, v:v) yielded in the isolation of 86.49 mg crystallized 1. Finally the colourless block crystals were washed with eluent C (Hex:EtOAc: 67:33, v:v) before being analyzed.

NMR analysis: ¹H and ¹³C NMR spectra were recorded at 293 K on a Varian UnityInova 400 NMR spectrometer with a 5 mm broadband probe. E-Notpterol was dissolved in chloroform-d (Aldrich, USA) and TMS was used as internal standard.

NMR results: ¹H NMR (CDCl₃, 400 MHz) δ 1.70 (3H, d, J = 1.2, H-50), 1.72 (3H, d, J = 1.2, H-48), 1.77 (3H, s, H-49), 2.22 (1H, dd, J = 13.7, 5.0, H-44b), 2.31 (1H, dd, J = 13.7, 8.2, H-44a), 4.52 (1H, m, H-45), 4.98 (2H, d, J = 6.9, H-41), 5.18 (1H, pseudo td, J = 8.4, 1.3, H-46), 5.65 (1H, pseudo dt, J = 6.7, 1.0, H-42), 6.28 (1H, d, J = 9.8, H-6), 6.98 (1H, dd, J = 2.4, 0.8, H-3), 7.16 (1H, s, H-9), 7.60 (1H, d, J = 2.4, H-2), 8.16 (1H, d, J = 9.8, H-5); ¹³C NMR (CDCl₃, 400 MHz) δ 17.0 (CH3, C-49), 18.2 (CH3, C-50), 25.7 (CH3, C-48), 47.7 (CH2, C-44), 66.4 (CH, C-45), 69.4 (CH2, C-41), 94.3 (CH, C-9), 105.0 (CH, C-3), 107.4 (C, C-14), 112.6 (CH, C-6), 114.0 (C, C-13), 122.4 (CH, C-42), 127.3 (CH, C-46), 135.6 (C, C-47), 139.5 (C, C-43), 139.5 (CH, C-5), 145.0 (CH, C-2), 148.7 (C, C-4), 152.6 (C, C-18), 158.1 (C, C-19), 161.3 (C, C-7).

LC—MS-analysis: Experiments were performed on a Thermo Finnigan Surveyor liquid chromatograph interfaced with a LCQ^TM Deca XP^PLUS mass detector. E-Notopterol was dissolved in methanol (HPLC grade, Merck, Darmstadt, Germany) and analyzed in the ESI+ mode under following conditions: Sheath gas flow: 70 units, ionization voltage: 5,50 kV, capillary voltage 15 V, tube lens offset: 50 V, capillary temperature: 623 K.

Computing details top

Data collection: local software; cell refinement: local software; data reduction: local software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: modified ORTEP (Johnson, 1965); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP plot (Johnson, 1965) showing the atomic numbering scheme. The probability ellipsoids are drawn at the 50% probability level.
	Fig. 2. Stereoscopic ORTEP plot (Johnson, 1965) of the packing. The atoms are drawn with arbitrary radii.

4-{[(2E)-5-hydroxy-3,7-dimethyl- octa-2,6-dien-1-yl]oxy}-7H-furo[3,2-g][1]benzopyran-7-one top

Crystal data top

C₂₁H₂₂O₅	Z = 2
M_r = 354.39	F(000) = 376
Triclinic, P1	D_x = 1.330 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 6.4317 (10) Å	Cell parameters from 60 reflections
b = 8.0912 (16) Å	θ = 16.0–19.8°
c = 17.206 (3) Å	µ = 0.09 mm⁻¹
α = 91.802 (15)°	T = 95 K
β = 94.240 (13)°	Block, colourless
γ = 97.473 (15)°	0.48 × 0.44 × 0.32 mm
V = 884.6 (3) Å³

Data collection top

Stoe four-circle diffractometer	R_int = 0.023
Radiation source: fine-focus sealed tube	θ_max = 26.0°, θ_min = 2.5°
Graphite monochromator	h = −7→7
ω–2θ scans	k = −9→1
4234 measured reflections	l = −21→21
3462 independent reflections	3 standard reflections every 100 reflections
2941 reflections with I > 2σ(I)	intensity decay: 0.4%

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	Only H-atom displacement parameters refined
S = 1.04	w = 1/[σ²(F_o²) + (0.0482P)² + 0.2588P] where P = (F_o² + 2F_c²)/3
3462 reflections	(Δ/σ)_max < 0.001
249 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂₁H₂₂O₅	γ = 97.473 (15)°
M_r = 354.39	V = 884.6 (3) Å³
Triclinic, P1	Z = 2
a = 6.4317 (10) Å	Mo Kα radiation
b = 8.0912 (16) Å	µ = 0.09 mm⁻¹
c = 17.206 (3) Å	T = 95 K
α = 91.802 (15)°	0.48 × 0.44 × 0.32 mm
β = 94.240 (13)°

Data collection top

Stoe four-circle diffractometer	R_int = 0.023
4234 measured reflections	3 standard reflections every 100 reflections
3462 independent reflections	intensity decay: 0.4%
2941 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.113	Only H-atom displacement parameters refined
S = 1.04	Δρ_max = 0.38 e Å⁻³
3462 reflections	Δρ_min = −0.21 e Å⁻³
249 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.

The non-hydrogen atoms were refined with anisotropic displacement parameters without any constraints. The H atoms of the 7H-Furo[3,2-g][1]benzopyran-7-one ring system were put at the external bisector of the C—C—C angle at a C—H distance of 0.95 Å and a common isotropic displacement parameter was refined (AFIX 43 of SHELXL97). The H atoms of the CH₂ groups were refined with common isotropic displacement parameters for the H atoms of the same group and idealized geometry with approximately tetrahedral angles and C—H distances of 0.99 Å (AFIX 23 of SHELXL97). The H atoms bonded to a C atom of a C=C double bond were put at the external bisector of the C—C—C angle at a C—H distance of 0.95 Å but the individual isotropic displacement parameters are free to refine (AFIX 43 of SHELXL97). The H atom of the tertiary C—H group was refined with an individual isotropic displacement parameter and all X—C—H angles equal at a C—H distance of 1.00 Å (AFIX 13 of SHELXL97). The H atoms of the methyl groups were refined with common isotropic displacement parameters for the H atoms of the same group and idealized geometry with tetrahedral angles, enabling rotation around the X—C bond, and C—H distances of 0.98 Å (AFIX 137 of SHELXL97). The H atom of the OH group was refined with a tetrahedral C—O—H angle, enabling rotation around the C—O bond, O—H distance of 0.84 Å, and with an individual isotropic displacement parameter (AFIX 147 of SHELXL97).

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

	x	y	z	U_iso*/U_eq
O1	0.08010 (16)	1.43591 (14)	0.41654 (6)	0.0244 (3)
C2	0.0927 (2)	1.43677 (19)	0.33658 (9)	0.0246 (3)
H2	−0.0037	1.4827	0.3016	0.028 (2)*
C3	0.2568 (2)	1.36524 (19)	0.31406 (9)	0.0226 (3)
H3	0.2957	1.3524	0.2622	0.028 (2)*
C4	0.5403 (2)	1.23232 (17)	0.40535 (8)	0.0177 (3)
C5	0.7767 (2)	1.13743 (18)	0.51262 (9)	0.0202 (3)
H5	0.8670	1.1018	0.4760	0.028 (2)*
C6	0.8224 (2)	1.11882 (19)	0.58937 (9)	0.0225 (3)
H6	0.9445	1.0707	0.6059	0.028 (2)*
C7	0.6889 (2)	1.17088 (19)	0.64707 (9)	0.0228 (3)
O7	0.71375 (18)	1.15883 (16)	0.71723 (6)	0.0305 (3)
O8	0.51411 (17)	1.24050 (14)	0.62003 (6)	0.0231 (3)
C9	0.2897 (2)	1.33880 (19)	0.52396 (9)	0.0216 (3)
H9	0.2045	1.3732	0.5626	0.028 (2)*
C13	0.3631 (2)	1.31129 (18)	0.38445 (8)	0.0185 (3)
C14	0.5942 (2)	1.21012 (17)	0.48527 (8)	0.0179 (3)
C18	0.4657 (2)	1.26325 (18)	0.54174 (8)	0.0189 (3)
C19	0.2464 (2)	1.36067 (18)	0.44558 (9)	0.0200 (3)
O4	0.66912 (16)	1.17002 (14)	0.35580 (6)	0.0223 (3)
C41	0.6201 (2)	1.17328 (19)	0.27226 (8)	0.0206 (3)
H411	0.6516	1.2880	0.2540	0.022 (3)*
H412	0.4695	1.1328	0.2584	0.022 (3)*
C42	0.7567 (2)	1.05985 (18)	0.23652 (8)	0.0197 (3)
H42	0.8956	1.0633	0.2601	0.030 (5)*
C43	0.7031 (2)	0.95436 (18)	0.17484 (8)	0.0198 (3)
C44	0.8569 (2)	0.84090 (19)	0.14954 (9)	0.0215 (3)
H441	0.9936	0.8725	0.1801	0.031 (3)*
H442	0.8797	0.8576	0.0939	0.031 (3)*
C45	0.7817 (3)	0.6553 (2)	0.16021 (9)	0.0247 (4)
H45	0.6569	0.6179	0.1228	0.026 (4)*
O5	0.7265 (2)	0.62481 (16)	0.23818 (7)	0.0342 (3)
H51	0.6537	0.6973	0.2528	0.068 (8)*
C46	0.9538 (3)	0.5518 (2)	0.14538 (9)	0.0246 (3)
H46	1.0863	0.5869	0.1731	0.022 (4)*
C47	0.9430 (3)	0.4165 (2)	0.09793 (9)	0.0251 (3)
C48	1.1328 (3)	0.3278 (2)	0.08976 (10)	0.0322 (4)
H481	1.2543	0.3891	0.1207	0.042 (3)*
H482	1.1628	0.3221	0.0348	0.042 (3)*
H483	1.1048	0.2146	0.1085	0.042 (3)*
C49	0.4927 (3)	0.9353 (2)	0.12808 (9)	0.0248 (3)
H491	0.4120	1.0230	0.1448	0.043 (3)*
H492	0.4150	0.8258	0.1365	0.043 (3)*
H493	0.5146	0.9448	0.0725	0.043 (3)*
C50	0.7499 (3)	0.3374 (2)	0.04907 (10)	0.0335 (4)
H501	0.6298	0.3945	0.0608	0.058 (4)*
H502	0.7204	0.2194	0.0609	0.058 (4)*
H503	0.7737	0.3470	−0.0063	0.058 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0215 (5)	0.0223 (6)	0.0295 (6)	0.0061 (4)	−0.0006 (4)	−0.0023 (5)
C2	0.0264 (8)	0.0193 (8)	0.0272 (8)	0.0028 (6)	−0.0037 (6)	0.0002 (6)
C3	0.0268 (8)	0.0172 (7)	0.0236 (8)	0.0043 (6)	−0.0013 (6)	−0.0002 (6)
C4	0.0202 (7)	0.0113 (7)	0.0212 (7)	0.0004 (6)	0.0036 (6)	−0.0027 (6)
C5	0.0224 (8)	0.0142 (7)	0.0234 (8)	0.0002 (6)	0.0025 (6)	−0.0003 (6)
C6	0.0241 (8)	0.0178 (7)	0.0247 (8)	0.0007 (6)	−0.0012 (6)	0.0025 (6)
C7	0.0239 (8)	0.0191 (8)	0.0227 (8)	−0.0053 (6)	−0.0015 (6)	0.0015 (6)
O7	0.0328 (6)	0.0363 (7)	0.0199 (6)	−0.0044 (5)	−0.0006 (5)	0.0032 (5)
O8	0.0251 (6)	0.0251 (6)	0.0183 (5)	0.0006 (5)	0.0026 (4)	−0.0005 (4)
C9	0.0199 (7)	0.0190 (8)	0.0254 (8)	−0.0001 (6)	0.0053 (6)	−0.0041 (6)
C13	0.0212 (7)	0.0118 (7)	0.0217 (7)	0.0011 (6)	0.0005 (6)	−0.0018 (6)
C14	0.0201 (7)	0.0120 (7)	0.0208 (7)	−0.0001 (6)	0.0014 (6)	−0.0016 (6)
C18	0.0224 (7)	0.0144 (7)	0.0185 (7)	−0.0026 (6)	0.0014 (6)	−0.0013 (6)
C19	0.0180 (7)	0.0131 (7)	0.0283 (8)	0.0016 (6)	0.0001 (6)	−0.0014 (6)
O4	0.0263 (6)	0.0255 (6)	0.0168 (5)	0.0100 (5)	0.0020 (4)	−0.0023 (4)
C41	0.0266 (8)	0.0184 (7)	0.0167 (7)	0.0033 (6)	0.0014 (6)	0.0002 (6)
C42	0.0217 (7)	0.0186 (7)	0.0192 (7)	0.0032 (6)	0.0022 (6)	0.0020 (6)
C43	0.0255 (8)	0.0163 (7)	0.0181 (7)	0.0032 (6)	0.0037 (6)	0.0038 (6)
C44	0.0277 (8)	0.0195 (8)	0.0180 (7)	0.0043 (6)	0.0043 (6)	−0.0008 (6)
C45	0.0281 (8)	0.0212 (8)	0.0256 (8)	0.0058 (7)	0.0039 (6)	0.0000 (6)
O5	0.0427 (7)	0.0292 (7)	0.0366 (7)	0.0163 (6)	0.0186 (6)	0.0099 (5)
C46	0.0267 (8)	0.0224 (8)	0.0253 (8)	0.0058 (7)	0.0028 (6)	0.0017 (6)
C47	0.0329 (9)	0.0202 (8)	0.0233 (8)	0.0049 (7)	0.0062 (6)	0.0053 (6)
C48	0.0444 (10)	0.0266 (9)	0.0290 (9)	0.0141 (8)	0.0090 (7)	0.0005 (7)
C49	0.0306 (9)	0.0237 (8)	0.0200 (7)	0.0047 (7)	−0.0004 (6)	−0.0013 (6)
C50	0.0424 (10)	0.0243 (9)	0.0322 (9)	−0.0008 (8)	0.0030 (8)	−0.0013 (7)

Geometric parameters (Å, º) top

O1—C19	1.3688 (18)	C41—H412	0.99
O1—C2	1.3843 (19)	C42—C43	1.336 (2)
C2—C3	1.343 (2)	C42—H42	0.95
C2—H2	0.95	C43—C49	1.509 (2)
C3—C13	1.454 (2)	C43—C44	1.512 (2)
C3—H3	0.95	C44—C45	1.537 (2)
C4—O4	1.3613 (18)	C44—H441	0.99
C4—C13	1.407 (2)	C44—H442	0.99
C4—C14	1.416 (2)	C45—O5	1.4336 (19)
C5—C6	1.349 (2)	C45—C46	1.504 (2)
C5—C14	1.436 (2)	C45—H45	1.00
C5—H5	0.95	O5—H51	0.84
C6—C7	1.447 (2)	C46—C47	1.337 (2)
C6—H6	0.95	C46—H46	0.95
C7—O7	1.2145 (19)	C47—C50	1.504 (2)
C7—O8	1.3788 (19)	C47—C48	1.507 (2)
O8—C18	1.3834 (18)	C48—H481	0.98
C9—C18	1.375 (2)	C48—H482	0.98
C9—C19	1.378 (2)	C48—H483	0.98
C9—H9	0.95	C49—H491	0.98
C13—C19	1.413 (2)	C49—H492	0.98
C14—C18	1.413 (2)	C49—H493	0.98
O4—C41	1.4504 (17)	C50—H501	0.98
C41—C42	1.499 (2)	C50—H502	0.98
C41—H411	0.99	C50—H503	0.98

C19—O1—C2	105.94 (12)	C43—C42—H42	116.7
C3—C2—O1	112.26 (14)	C41—C42—H42	116.7
C3—C2—H2	123.9	C42—C43—C49	124.47 (14)
O1—C2—H2	123.9	C42—C43—C44	119.56 (14)
C2—C3—C13	106.62 (14)	C49—C43—C44	115.95 (13)
C2—C3—H3	126.7	C43—C44—C45	113.08 (13)
C13—C3—H3	126.7	C43—C44—H441	109.0
O4—C4—C13	126.59 (13)	C45—C44—H441	109.0
O4—C4—C14	114.47 (13)	C43—C44—H442	109.0
C13—C4—C14	118.94 (13)	C45—C44—H442	109.0
C6—C5—C14	121.15 (14)	H441—C44—H442	107.8
C6—C5—H5	119.4	O5—C45—C46	106.58 (13)
C14—C5—H5	119.4	O5—C45—C44	111.88 (13)
C5—C6—C7	121.23 (15)	C46—C45—C44	110.45 (13)
C5—C6—H6	119.4	O5—C45—H45	109.3
C7—C6—H6	119.4	C46—C45—H45	109.3
O7—C7—O8	116.20 (14)	C44—C45—H45	109.3
O7—C7—C6	126.77 (15)	C45—O5—H51	109.5
O8—C7—C6	117.03 (13)	C47—C46—C45	127.87 (15)
C7—O8—C18	122.82 (12)	C47—C46—H46	116.1
C18—C9—C19	114.72 (14)	C45—C46—H46	116.1
C18—C9—H9	122.6	C46—C47—C50	125.44 (16)
C19—C9—H9	122.6	C46—C47—C48	120.82 (15)
C4—C13—C19	117.12 (13)	C50—C47—C48	113.73 (15)
C4—C13—C3	138.18 (14)	C47—C48—H481	109.5
C19—C13—C3	104.68 (13)	C47—C48—H482	109.5
C18—C14—C4	119.34 (13)	H481—C48—H482	109.5
C18—C14—C5	117.56 (13)	C47—C48—H483	109.5
C4—C14—C5	123.09 (13)	H481—C48—H483	109.5
C9—C18—O8	116.11 (13)	H482—C48—H483	109.5
C9—C18—C14	123.71 (14)	C43—C49—H491	109.5
O8—C18—C14	120.18 (13)	C43—C49—H492	109.5
O1—C19—C9	123.36 (14)	H491—C49—H492	109.5
O1—C19—C13	110.49 (13)	C43—C49—H493	109.5
C9—C19—C13	126.15 (14)	H491—C49—H493	109.5
C4—O4—C41	119.53 (11)	H492—C49—H493	109.5
O4—C41—C42	105.47 (12)	C47—C50—H501	109.5
O4—C41—H411	110.6	C47—C50—H502	109.5
C42—C41—H411	110.6	H501—C50—H502	109.5
O4—C41—H412	110.6	C47—C50—H503	109.5
C42—C41—H412	110.6	H501—C50—H503	109.5
H411—C41—H412	108.8	H502—C50—H503	109.5
C43—C42—C41	126.62 (14)

C19—O1—C2—C3	0.41 (17)	C4—C14—C18—O8	179.09 (12)
O1—C2—C3—C13	0.19 (18)	C5—C14—C18—O8	−1.7 (2)
C14—C5—C6—C7	0.2 (2)	C2—O1—C19—C9	178.89 (14)
C5—C6—C7—O7	179.33 (15)	C2—O1—C19—C13	−0.87 (16)
C5—C6—C7—O8	−0.2 (2)	C18—C9—C19—O1	−178.88 (13)
O7—C7—O8—C18	179.60 (13)	C18—C9—C19—C13	0.9 (2)
C6—C7—O8—C18	−0.8 (2)	C4—C13—C19—O1	179.76 (12)
O4—C4—C13—C19	177.50 (13)	C3—C13—C19—O1	0.98 (16)
C14—C4—C13—C19	−1.4 (2)	C4—C13—C19—C9	0.0 (2)
O4—C4—C13—C3	−4.3 (3)	C3—C13—C19—C9	−178.78 (14)
C14—C4—C13—C3	176.88 (16)	C13—C4—O4—C41	−3.8 (2)
C2—C3—C13—C4	−179.08 (17)	C14—C4—O4—C41	175.09 (12)
C2—C3—C13—C19	−0.70 (16)	C4—O4—C41—C42	−166.21 (12)
O4—C4—C14—C18	−177.18 (12)	O4—C41—C42—C43	141.31 (15)
C13—C4—C14—C18	1.8 (2)	C41—C42—C43—C49	2.1 (2)
O4—C4—C14—C5	3.7 (2)	C41—C42—C43—C44	−176.19 (14)
C13—C4—C14—C5	−177.31 (13)	C42—C43—C44—C45	113.54 (16)
C6—C5—C14—C18	0.8 (2)	C49—C43—C44—C45	−64.89 (17)
C6—C5—C14—C4	179.90 (14)	C43—C44—C45—O5	−53.12 (17)
C19—C9—C18—O8	179.60 (12)	C43—C44—C45—C46	−171.68 (13)
C19—C9—C18—C14	−0.4 (2)	O5—C45—C46—C47	109.83 (18)
C7—O8—C18—C9	−178.14 (13)	C44—C45—C46—C47	−128.43 (17)
C7—O8—C18—C14	1.8 (2)	C45—C46—C47—C50	−0.7 (3)
C4—C14—C18—C9	−0.9 (2)	C45—C46—C47—C48	179.69 (15)
C5—C14—C18—C9	178.22 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H51···O8ⁱ	0.84	2.57	3.2193 (16)	135

Symmetry code: (i) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₂O₅
M_r	354.39
Crystal system, space group	Triclinic, P1
Temperature (K)	95
a, b, c (Å)	6.4317 (10), 8.0912 (16), 17.206 (3)
α, β, γ (°)	91.802 (15), 94.240 (13), 97.473 (15)
V (Å³)	884.6 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.48 × 0.44 × 0.32

Data collection
Diffractometer	Stoe four-circle diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4234, 3462, 2941
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.113, 1.04
No. of reflections	3462
No. of parameters	249
H-atom treatment	Only H-atom displacement parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.21

Computer programs: local software, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), modified ORTEP (Johnson, 1965).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H51···O8ⁱ	0.84	2.57	3.2193 (16)	134.5

Symmetry code: (i) −x+1, −y+2, −z+1.

Acknowledgements

Funding provided by the Austrian Science Fund (FWF) within project S107 (Drugs from Nature Targeting Inflammation) is gratefully acknowledged.

References

Chemical Abstract Service (2009). The SciFinder database. Chemical Abstracts Service, Columbus, Ohio, USA. Google Scholar
Hasegawa, A., Nakamura, H., Watanabe, T., Okuyama, E., Ohmori, S., Ishikawa, T. & Kitada, M. (1999). Biol. Pharm. Bull. 22, 725–726. Web of Science CrossRef PubMed CAS Google Scholar
Johnson, C. K. (1965). ORTEP. Report ORNL-3794. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xiao, Y., Sun, Y. & Liu, K. (1994). Zhongguo Zhongyao Zazhi, 19, 421–422. CAS PubMed Google Scholar
Yang, X., Yan, Z., Gu, Z., Zhou, G., Hattori, M. & Namba, T. (1994). Zhongguo Yaoxue Zazhi, 29, 141–143. CAS Google Scholar