Fraxinellone

Gu, H.-M.; Xu, H.; Zhong, Z.-Z.; Zhu, H.-L.; Li, Q.-S.

doi:10.1107/S1600536811018393

organic compounds

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Volume 67| Part 6| June 2011| Page o1472

doi:10.1107/S1600536811018393

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Fraxinellone

Hong-Mei Gu,^a Hao Xu,^a Zhao-Zhao Zhong,^a Hai-Liang Zhu ^a and Qing-Shan Li ^a ^*

^aJiangsu Chiatai Tianqing Pharmaceutical Co. Ltd, Nanjing 210042, People's Repulic of China, and, State Key Laboratory of Pharmaceutical Biotechnology, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: benbenshell@yahoo.com.cn

(Received 27 April 2011; accepted 15 May 2011; online 20 May 2011)

In the title compound, C₁₄H₁₆O₃ [systematic name: (3R*,3aR*)-3-(3-furanyl)-3a,7-dimethyl-3a,4,5,6-tetrahydro-2-benzofuran-1(3H)-one], the pendant methyl and furan groups attached to the stereogenic centres lie to the same side of the fused ring system. The dihedral angle between the five-membered rings is 74.8 (2)°; the fused five-membered ring adopts a twisted conformation. In the crystal, molecules are linked by weak C—H⋯O interactions, which generate [100] chains.

Related literature

For background to fraxinellone and its biological activity, see: Kim et al. (2009 ); Sun et al. (2009 ); Liu et al. (2009 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₁₆O₃
M_r = 232.27
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.940 (3) Å
b = 12.661 (6) Å
c = 15.921 (7) Å
V = 1197.3 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.982, T_max = 0.984
10397 measured reflections
1733 independent reflections
1331 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.113
S = 1.07
1733 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O1ⁱ	0.98	2.58	3.510 (3)	158
Symmetry code: (i) x-1, y, z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXL97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811018393/hb5863sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811018393/hb5863Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811018393/hb5863Isup3.cml

checkCIF report

Comment top

There has been much research interest in fraxinellone due to its biological activities (Kim et al. (2009); Sun et al. (2009); Liu et al. (2009)). In this work, we report here the crystal structure of the title compound, (I). In (I), all bond lengths are within normal ranges (Allen et al., 1987) (Fig. 1). The dihedral angle between the C1—C2—C7—C8—O2 and C12—C11—C14—C13—O3 rings is 74.8 (2)°.

Related literature top

For background to fraxinellone and its biological activity, see: Kim et al. (2009); Sun et al. (2009); Liu et al. (2009). For standard bond lengths, see: Allen et al. (1987).

Experimental top

In order to extract the fraxinellone with bioactivity containing in Dictamnus dasycarpus Turks, 100 g/L milk of lime wetting plant material, was extracted by using refluent extract method with petroleum ether as a solvent. The residue was separated with methanol and petroleum ether, and recrystallized in methanol. It was further purified on a silica gel column. Crystals suitable for X-ray structure analysis were obtained by slow evaporation of a solution in methanol at room temperature.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids.

(3R*,3aR*)-3-(3-furanyl)-3a,4,5,6- tetrahydro-3a,7-dimethyl-2-benzofuran-1(3H)-one top

Crystal data top

C₁₄H₁₆O₃	F(000) = 496
M_r = 232.27	D_x = 1.288 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 5.940 (3) Å	θ = 9–12°
b = 12.661 (6) Å	µ = 0.09 mm⁻¹
c = 15.921 (7) Å	T = 298 K
V = 1197.3 (9) Å³	Block, colorless
Z = 4	0.20 × 0.20 × 0.18 mm

Data collection top

Bruker SMART CCD diffractometer	1733 independent reflections
Radiation source: fine-focus sealed tube	1331 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ϕ and ω scans	θ_max = 28.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −7→7
T_min = 0.982, T_max = 0.984	k = −17→16
10397 measured reflections	l = −19→21

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0425P)² + 0.1558P] where P = (F_o² + 2F_c²)/3
1733 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₄H₁₆O₃	V = 1197.3 (9) Å³
M_r = 232.27	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.940 (3) Å	µ = 0.09 mm⁻¹
b = 12.661 (6) Å	T = 298 K
c = 15.921 (7) Å	0.20 × 0.20 × 0.18 mm

Data collection top

Bruker SMART CCD diffractometer	1733 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1331 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.984	R_int = 0.049
10397 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.07	Δρ_max = 0.12 e Å⁻³
1733 reflections	Δρ_min = −0.17 e Å⁻³
156 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O1	0.5425 (3)	−0.10394 (15)	0.61505 (12)	0.0558 (5)
O2	0.2594 (3)	0.00000 (13)	0.65310 (9)	0.0423 (4)
O3	−0.2584 (5)	0.24662 (18)	0.72681 (14)	0.0806 (8)
C1	0.3749 (4)	−0.05682 (18)	0.59460 (15)	0.0391 (5)
C2	0.2628 (4)	−0.04409 (17)	0.51292 (14)	0.0377 (5)
C3	0.2806 (5)	−0.10573 (18)	0.44505 (15)	0.0428 (6)
C4	0.1270 (5)	−0.0894 (2)	0.37091 (17)	0.0571 (7)
H4A	0.0334	−0.1517	0.3649	0.069*
H4B	0.2190	−0.0840	0.3208	0.069*
C5	−0.0254 (5)	0.0067 (2)	0.37495 (17)	0.0583 (7)
H5A	−0.1572	−0.0058	0.3404	0.070*
H5B	0.0539	0.0671	0.3520	0.070*
C6	−0.1009 (4)	0.0323 (2)	0.46465 (16)	0.0488 (6)
H6A	−0.1916	0.0960	0.4645	0.059*
H6B	−0.1925	−0.0251	0.4862	0.059*
C7	0.1041 (4)	0.04793 (17)	0.52105 (13)	0.0355 (5)
C8	0.0486 (4)	0.03908 (17)	0.61578 (14)	0.0364 (5)
H8	−0.0667	−0.0156	0.6228	0.044*
C9	0.4404 (5)	−0.1978 (2)	0.4381 (2)	0.0599 (8)
H9A	0.5589	−0.1806	0.3995	0.090*
H9B	0.3603	−0.2587	0.4181	0.090*
H9C	0.5037	−0.2127	0.4923	0.090*
C10	0.2300 (5)	0.15067 (19)	0.50129 (15)	0.0466 (6)
H10A	0.3577	0.1572	0.5379	0.070*
H10B	0.1311	0.2097	0.5096	0.070*
H10C	0.2802	0.1495	0.4440	0.070*
C11	−0.0265 (4)	0.13529 (19)	0.66193 (14)	0.0416 (6)
C12	−0.2403 (6)	0.1508 (2)	0.68932 (16)	0.0563 (7)
H12	−0.3574	0.1026	0.6833	0.068*
C13	−0.0487 (6)	0.2921 (2)	0.72441 (18)	0.0579 (8)
H13	−0.0116	0.3577	0.7467	0.069*
C14	0.0930 (6)	0.2275 (2)	0.68509 (17)	0.0542 (7)
H14	0.2445	0.2406	0.6746	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0482 (11)	0.0579 (10)	0.0612 (11)	0.0135 (10)	−0.0039 (10)	0.0022 (9)
O2	0.0457 (9)	0.0438 (8)	0.0372 (8)	0.0068 (8)	0.0002 (8)	0.0015 (7)
O3	0.101 (2)	0.0835 (16)	0.0576 (12)	0.0376 (17)	0.0124 (14)	−0.0099 (11)
C1	0.0405 (13)	0.0328 (11)	0.0441 (13)	−0.0013 (11)	0.0046 (11)	0.0044 (10)
C2	0.0383 (13)	0.0356 (11)	0.0391 (12)	−0.0052 (11)	0.0047 (11)	0.0025 (9)
C3	0.0415 (14)	0.0389 (12)	0.0480 (14)	−0.0062 (11)	0.0090 (12)	−0.0047 (10)
C4	0.0623 (18)	0.0652 (16)	0.0438 (15)	−0.0026 (16)	0.0025 (14)	−0.0105 (13)
C5	0.0666 (19)	0.0645 (16)	0.0438 (14)	0.0014 (16)	−0.0078 (14)	−0.0009 (13)
C6	0.0476 (15)	0.0539 (15)	0.0449 (14)	0.0050 (13)	−0.0071 (12)	−0.0008 (12)
C7	0.0375 (12)	0.0348 (11)	0.0342 (11)	0.0006 (10)	0.0034 (10)	0.0013 (9)
C8	0.0351 (12)	0.0373 (11)	0.0369 (11)	0.0000 (10)	0.0024 (10)	0.0023 (9)
C9	0.0583 (19)	0.0508 (15)	0.0708 (19)	0.0022 (15)	0.0055 (16)	−0.0183 (14)
C10	0.0561 (16)	0.0385 (11)	0.0451 (13)	−0.0066 (13)	0.0066 (14)	0.0048 (10)
C11	0.0467 (15)	0.0454 (13)	0.0326 (11)	0.0058 (12)	0.0009 (11)	0.0024 (10)
C12	0.0607 (18)	0.0642 (16)	0.0439 (14)	0.0099 (16)	0.0075 (16)	−0.0036 (13)
C13	0.082 (2)	0.0455 (14)	0.0465 (15)	0.0112 (16)	−0.0031 (16)	−0.0107 (12)
C14	0.0634 (19)	0.0508 (14)	0.0485 (15)	−0.0008 (15)	−0.0041 (15)	−0.0052 (12)

Geometric parameters (Å, º) top

O1—C1	1.205 (3)	C6—H6B	0.9700
O2—C1	1.362 (3)	C7—C10	1.533 (3)
O2—C8	1.471 (3)	C7—C8	1.548 (3)
O3—C12	1.357 (3)	C8—C11	1.491 (3)
O3—C13	1.373 (4)	C8—H8	0.9800
C1—C2	1.470 (3)	C9—H9A	0.9600
C2—C3	1.337 (3)	C9—H9B	0.9600
C2—C7	1.504 (3)	C9—H9C	0.9600
C3—C4	1.506 (4)	C10—H10A	0.9600
C3—C9	1.507 (4)	C10—H10B	0.9600
C4—C5	1.518 (4)	C10—H10C	0.9600
C4—H4A	0.9700	C11—C12	1.357 (4)
C4—H4B	0.9700	C11—C14	1.415 (4)
C5—C6	1.531 (4)	C12—H12	0.9300
C5—H5A	0.9700	C13—C14	1.331 (4)
C5—H5B	0.9700	C13—H13	0.9300
C6—C7	1.526 (3)	C14—H14	0.9300
C6—H6A	0.9700

C1—O2—C8	109.29 (17)	C6—C7—C8	113.2 (2)
C12—O3—C13	106.9 (3)	C10—C7—C8	111.41 (18)
O1—C1—O2	119.5 (2)	O2—C8—C11	109.30 (19)
O1—C1—C2	131.9 (2)	O2—C8—C7	103.70 (17)
O2—C1—C2	108.6 (2)	C11—C8—C7	119.00 (18)
C3—C2—C1	128.0 (2)	O2—C8—H8	108.1
C3—C2—C7	124.8 (2)	C11—C8—H8	108.1
C1—C2—C7	107.02 (18)	C7—C8—H8	108.1
C2—C3—C4	120.4 (2)	C3—C9—H9A	109.5
C2—C3—C9	124.1 (3)	C3—C9—H9B	109.5
C4—C3—C9	115.5 (2)	H9A—C9—H9B	109.5
C3—C4—C5	116.0 (2)	C3—C9—H9C	109.5
C3—C4—H4A	108.3	H9A—C9—H9C	109.5
C5—C4—H4A	108.3	H9B—C9—H9C	109.5
C3—C4—H4B	108.3	C7—C10—H10A	109.5
C5—C4—H4B	108.3	C7—C10—H10B	109.5
H4A—C4—H4B	107.4	H10A—C10—H10B	109.5
C4—C5—C6	112.6 (2)	C7—C10—H10C	109.5
C4—C5—H5A	109.1	H10A—C10—H10C	109.5
C6—C5—H5A	109.1	H10B—C10—H10C	109.5
C4—C5—H5B	109.1	C12—C11—C14	105.5 (2)
C6—C5—H5B	109.1	C12—C11—C8	123.8 (3)
H5A—C5—H5B	107.8	C14—C11—C8	130.7 (2)
C7—C6—C5	110.0 (2)	C11—C12—O3	110.2 (3)
C7—C6—H6A	109.7	C11—C12—H12	124.9
C5—C6—H6A	109.7	O3—C12—H12	124.9
C7—C6—H6B	109.7	C14—C13—O3	109.2 (2)
C5—C6—H6B	109.7	C14—C13—H13	125.4
H6A—C6—H6B	108.2	O3—C13—H13	125.4
C2—C7—C6	110.41 (19)	C13—C14—C11	108.2 (3)
C2—C7—C10	109.49 (19)	C13—C14—H14	125.9
C6—C7—C10	112.3 (2)	C11—C14—H14	125.9
C2—C7—C8	99.28 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O1ⁱ	0.98	2.58	3.510 (3)	158

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₆O₃
M_r	232.27
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	5.940 (3), 12.661 (6), 15.921 (7)
V (Å³)	1197.3 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.982, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	10397, 1733, 1331
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.671

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.113, 1.07
No. of reflections	1733
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.17

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O1ⁱ	0.98	2.58	3.510 (3)	158

Symmetry code: (i) x−1, y, z.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kim, J. H., Park, Y. M., Shin, J. S., Park, S. J., Choi, J. H., Jung, H. J., Park, H. J. & Lee, K. T. (2009). Biol. Pharm. Bull. pp. 1062–1068. CrossRef Google Scholar
Liu, Z. L., Ho, S. H. & Goh, S. H. (2009). Insect Sci., pp. 147–155. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, Y., Qin, Y., Gong, F. Y., Wu, X. F., Hua, Z. C., Chen, T. & Xu, Q. (2009). Biochem. Pharmacol. pp. 1717–1724. CrossRef Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1472

doi:10.1107/S1600536811018393

Open

access