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Acta Cryst. (2009). E65, o2387    [ doi:10.1107/S1600536809034485 ]

9-Methoxy-6a,11a-dimethyl-6a,11a-dihydro-6H-1-benzofuro[3,2-c]chromen-3-ol from Dalbergia oliveri

S. Deesamer, W. Chavasiri, N. Chaichit, N. Muangsin and U. Kokpol

Abstract top

The title compound, commonly known as (+)-(6aS,11aS)-medicarpin, C16H14O4, was isolated from Dalbergia oliveri and displays a rigid molecule consisting of four fused rings. The benzofuran system is inclined at an angle of 76.49 (2)° with respect to the chroman unit. The compound exists as a polymeric chain arising from intermolecular O-H...O bonding.

Comment top

Dalbergia Oliveri Gamble is widely found in Thailand and used in traditional Thai medicine for treament of chronic ulcer. One of major compositions of CH2Cl2 crude products extracted from the heartwoods of Dalbergia Oliveri (Deesamer et al., 2007) was (+)(6aS,11aS)-Medicarpin. It was identified as phytoalexin (Hargreaves et al., 1976).

The rigid molecule of the title compound consists of four fused rings adopts a bent-shaped conformation. The benzofuran ring system is inclined at the angle of 76.49 (2)° with respect to the chroman moiety. The tetrahydropyranyl group adopts an envelope conformation with atom C6 deviates from the plane by 0.4144 Å.

The compound exists as a polymeric chain arising from intermolecular O—H···O bonding.

Related literature top

For general background, see: Deesamer et al. (2007); Hargreaves et al. (1976). For a related structure, see: Aree et al. (2003).

Experimental top

Four kilograms of dried and powder heartwoods of D. oliveri were extracted with hexane. The marc was then extracted with CH2Cl2, EtOAc and MeOH, respectively. The CH2Cl2 crudeextract was subjected to silica gel colume chromatography eluting with 60%EtOAc:Hexane to afford the title compound (3.92 g). The suitable single crystals of the title compound were recrystallized from acetone-water as colourless needle crystals.

m.p. 132.0–133.5°C; m/z: 270[M+]

The specific rotation of D3 as [α]D+ 223.1° (c 0.16 in acetone, at 20°C) indicated the absolute configuration to be (+)(6aS,11aS)-medicarpin.

1H-NMR (CDCl3): δ (p.p.m.) 3.55(1H,m,H-6a), 3.65 (1H, dd, J =10.9 and 10.9 Hz, H-6ax), 4.26 (1H, dd, J = 4.8, 10.9 Hz, H-6eq) and 5.23 (1H, d, J = 6.7 Hz, H-116a),

Refinement top

All non-hydrogen atoms were anisotropically refined. The hydrogen atoms were positioned geometrically and refined using a riding model, with C—H = 0.93Å (aromatic), 0.97Å (CH2) and 0.98Å (CH3), and O—H = 0.82 Å, and Uiso(H) = 1.2Ueq (Caromatic), 1.5Ueq (CCH2), 1.5Ueq (CCH3) and 1.2Ueq (CO), respectively. In the structure, Friedel pairs [1949] were merged and the stereochemistry assumed from the specific rotation and the previously reported structure (Deesamer et al. 2007).

Computing details top

Data collection: SMART (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); 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: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. View of the title compound (50% probability displacement ellipsoids)
[Figure 2] Fig. 2. Packing diagram of a polymeric hydrogen bonding chain along the c axis.
9-Methoxy-6a,11a-dimethyl-6a,11a-dihydro-6H-\ 1-benzofuro[3,2-c]chromen-3-ol from Dalbergia Oliveri top
Crystal data top
C16H14O4Z = 2
Mr = 270.27F(000) = 284
Monoclinic, P21Dx = 1.379 Mg m−3
Hall symbol: P 2ybMo Kα radiation, λ = 0.71073 Å
a = 6.6289 (3) ŵ = 0.10 mm−1
b = 8.7963 (4) ÅT = 293 K
c = 11.3150 (5) ÅNeedle, colourless
β = 99.482 (1)°0.40 × 0.25 × 0.20 mm
V = 650.76 (5) Å3
Data collection top
Bruker SMART
diffractometer		Rint = 0.013
Radiation source: Moθmax = 30.4°, θmin = 1.8°
ω scansh = −7→9
4783 measured reflectionsk = −12→12
3198 independent reflectionsl = −15→13
1949 reflections with I > 2σ(I)
Refinement top
Refinement on F21 restraint
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.034 w = 1/[σ2(Fo2) + (0.0583P)2 + 0.0162P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.093(Δ/σ)max < 0.001
S = 1.09Δρmax = 0.16 e Å−3
1949 reflectionsΔρmin = −0.18 e Å−3
182 parameters
Crystal data top
C16H14O4V = 650.76 (5) Å3
Mr = 270.27Z = 2
Monoclinic, P21Mo Kα radiation
a = 6.6289 (3) ŵ = 0.10 mm−1
b = 8.7963 (4) ÅT = 293 K
c = 11.3150 (5) Å0.40 × 0.25 × 0.20 mm
β = 99.482 (1)°
Data collection top
Bruker SMART
diffractometer		1949 reflections with I > 2σ(I)
4783 measured reflectionsRint = 0.013
3198 independent reflectionsθmax = 30.4°
Refinement top
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.093Δρmax = 0.16 e Å−3
S = 1.09Δρmin = −0.18 e Å−3
1949 reflectionsAbsolute structure: ?
182 parametersFlack parameter: ?
1 restraintRogers parameter: ?
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
xyzUiso*/Ueq
C10.0057 (2)0.4390 (2)0.69102 (16)0.0414 (4)
H1−0.12520.3980.67360.05*
C20.0496 (3)0.5393 (3)0.78509 (16)0.0458 (4)
H2−0.05120.56640.82940.055*
C30.2455 (3)0.6001 (2)0.81356 (14)0.0413 (4)
C40.3960 (3)0.5576 (2)0.74813 (15)0.0399 (4)
H40.52780.59620.76780.048*
C4A0.3482 (2)0.45666 (19)0.65285 (14)0.0351 (3)
C60.4820 (3)0.2767 (2)0.53202 (17)0.0426 (4)
H6A0.49180.19640.59150.051*
H6B0.59280.26320.48670.051*
C6A0.2800 (2)0.26311 (19)0.44829 (15)0.0365 (3)
H6A10.26690.16010.41490.044*
C6B0.2447 (2)0.37674 (19)0.34730 (14)0.0338 (3)
C70.3662 (3)0.4270 (2)0.26630 (15)0.0393 (3)
H70.50070.39370.27230.047*
C80.2854 (3)0.5275 (2)0.17639 (16)0.0424 (4)
H80.3670.56330.1230.051*
C90.0829 (3)0.5752 (2)0.16556 (14)0.0388 (4)
C10−0.0419 (3)0.5288 (2)0.24674 (15)0.0374 (3)
H10−0.17640.56210.24090.045*
C10A0.0455 (2)0.43038 (19)0.33679 (13)0.0332 (3)
C11A0.0957 (2)0.29610 (19)0.51234 (15)0.0363 (3)
H11A0.03820.20020.53580.044*
C11B0.1513 (2)0.39649 (18)0.62068 (14)0.0343 (3)
C12−0.1997 (3)0.7026 (3)0.04448 (19)0.0579 (5)
H12A−0.22660.7714−0.02210.087*
H12B−0.24470.74740.1130.087*
H12C−0.27190.60910.02440.087*
O10.50439 (17)0.42138 (16)0.59175 (11)0.0436 (3)
O2−0.05777 (17)0.37602 (17)0.42345 (10)0.0401 (3)
O30.0152 (2)0.67276 (19)0.07158 (11)0.0518 (4)
O40.2992 (2)0.7012 (2)0.90549 (12)0.0550 (4)
H4A0.21020.70280.94790.083*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0296 (7)0.0524 (10)0.0410 (8)−0.0031 (7)0.0021 (6)0.0049 (8)
C20.0390 (8)0.0594 (11)0.0391 (8)0.0030 (8)0.0070 (7)0.0028 (8)
C30.0482 (9)0.0424 (9)0.0321 (7)−0.0012 (7)0.0026 (6)0.0048 (7)
C40.0368 (7)0.0448 (9)0.0372 (7)−0.0089 (6)0.0034 (6)0.0037 (7)
C4A0.0323 (7)0.0385 (8)0.0343 (7)−0.0031 (6)0.0045 (6)0.0059 (6)
C60.0361 (7)0.0445 (10)0.0460 (9)0.0054 (7)0.0030 (7)0.0002 (7)
C6A0.0372 (8)0.0295 (7)0.0414 (8)0.0010 (6)0.0022 (6)−0.0007 (6)
C6B0.0347 (7)0.0306 (7)0.0354 (7)0.0000 (6)0.0039 (6)−0.0039 (6)
C70.0361 (7)0.0411 (8)0.0420 (8)0.0012 (6)0.0102 (6)−0.0054 (7)
C80.0455 (9)0.0459 (9)0.0379 (8)−0.0007 (7)0.0130 (7)−0.0007 (7)
C90.0474 (9)0.0392 (9)0.0296 (7)0.0014 (7)0.0055 (6)−0.0027 (6)
C100.0359 (7)0.0423 (8)0.0331 (7)0.0048 (6)0.0035 (6)−0.0023 (6)
C10A0.0336 (7)0.0359 (7)0.0301 (6)−0.0033 (6)0.0049 (5)−0.0032 (6)
C11A0.0351 (7)0.0338 (8)0.0384 (8)−0.0057 (6)0.0010 (6)0.0056 (6)
C11B0.0310 (6)0.0360 (8)0.0342 (7)−0.0033 (6)0.0004 (5)0.0071 (6)
C120.0621 (12)0.0648 (13)0.0431 (9)0.0143 (11)−0.0022 (9)0.0089 (9)
O10.0305 (5)0.0527 (8)0.0482 (6)−0.0086 (5)0.0087 (4)−0.0075 (6)
O20.0299 (5)0.0536 (7)0.0358 (5)−0.0032 (5)0.0020 (4)0.0073 (5)
O30.0604 (8)0.0588 (9)0.0363 (6)0.0084 (7)0.0076 (5)0.0106 (6)
O40.0639 (9)0.0619 (9)0.0394 (7)−0.0071 (7)0.0088 (6)−0.0089 (6)
Geometric parameters (Å, °) top
C1—C21.376 (3)C6B—C10A1.389 (2)
C1—C11B1.399 (2)C7—C81.387 (3)
C1—H10.93C7—H70.93
C2—C31.393 (3)C8—C91.393 (2)
C2—H20.93C8—H80.93
C3—O41.370 (2)C9—O31.382 (2)
C3—C41.388 (3)C9—C101.395 (2)
C4—C4A1.392 (2)C10—C10A1.389 (2)
C4—H40.93C10—H100.93
C4A—O11.372 (2)C10A—O21.3709 (19)
C4A—C11B1.400 (2)C11A—O21.484 (2)
C6—O11.437 (2)C11A—C11B1.507 (2)
C6—C6A1.512 (2)C11A—H11A0.98
C6—H6A0.97C12—O31.431 (3)
C6—H6B0.97C12—H12A0.96
C6A—C6B1.507 (2)C12—H12B0.96
C6A—C11A1.547 (2)C12—H12C0.96
C6A—H6A10.98O4—H4A0.82
C6B—C71.389 (2)
C2—C1—C11B122.26 (15)C6B—C7—H7120.3
C2—C1—H1118.9C7—C8—C9120.45 (16)
C11B—C1—H1118.9C7—C8—H8119.8
C1—C2—C3119.68 (17)C9—C8—H8119.8
C1—C2—H2120.2O3—C9—C8116.15 (16)
C3—C2—H2120.2O3—C9—C10122.38 (15)
O4—C3—C4117.40 (16)C8—C9—C10121.46 (16)
O4—C3—C2122.73 (17)C10A—C10—C9116.39 (15)
C4—C3—C2119.87 (17)C10A—C10—H10121.8
C3—C4—C4A119.56 (15)C9—C10—H10121.8
C3—C4—H4120.2O2—C10A—C6B113.57 (14)
C4A—C4—H4120.2O2—C10A—C10123.03 (14)
O1—C4A—C4116.13 (14)C6B—C10A—C10123.39 (15)
O1—C4A—C11B122.15 (14)O2—C11A—C11B108.81 (14)
C4—C4A—C11B121.72 (14)O2—C11A—C6A106.09 (13)
O1—C6—C6A112.14 (14)C11B—C11A—C6A112.62 (13)
O1—C6—H6A109.2O2—C11A—H11A109.7
C6A—C6—H6A109.2C11B—C11A—H11A109.7
O1—C6—H6B109.2C6A—C11A—H11A109.7
C6A—C6—H6B109.2C1—C11B—C4A116.87 (15)
H6A—C6—H6B107.9C1—C11B—C11A121.33 (14)
C6B—C6A—C6115.68 (14)C4A—C11B—C11A121.74 (14)
C6B—C6A—C11A101.24 (12)O3—C12—H12A109.5
C6—C6A—C11A112.20 (14)O3—C12—H12B109.5
C6B—C6A—H6A1109.1H12A—C12—H12B109.5
C6—C6A—H6A1109.1O3—C12—H12C109.5
C11A—C6A—H6A1109.1H12A—C12—H12C109.5
C7—C6B—C10A118.82 (15)H12B—C12—H12C109.5
C7—C6B—C6A132.64 (14)C4A—O1—C6114.15 (13)
C10A—C6B—C6A108.46 (13)C10A—O2—C11A106.43 (12)
C8—C7—C6B119.42 (15)C9—O3—C12117.65 (15)
C8—C7—H7120.3C3—O4—H4A109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O3i0.822.072.882 (2)169
Symmetry codes: (i) x, y, z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O3i0.822.072.882 (2)169
Symmetry codes: (i) x, y, z+1.
Acknowledgements top

The authors gratefully acknowledge funding from the Royal Golden Jubilee PhD program (RGJ), the A1–B1 project and the Faculty of Science of Chulalongkorn University.

references
References top

Aree, T., Tip-pyang, S., Seesukphronrarak, S. & Chaichit, N. (2003). Acta Cryst. E59, o363–o365

Bruker (2006). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.

Deesamer, S., Kokpola, U., Chavasiria, W., Douillardb, S., Peyrotb, V., Vidalc, N. & Combesc, S. (2007). Tetrahedron, 63, 12986–12993.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Hargreaves, J. A., Mansfield, J. W. & Coxon, D. T. (1976). Nature (London), 262, 318–319.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.