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

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

doi:10.1107/S1600536809034485

organic compounds

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Volume 65| Part 10| October 2009| Page o2387

doi:10.1107/S1600536809034485

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

Sujittra Deesamer,^a Warinthorn Chavasiri,^a ^* Narongsak Chaichit,^b Nongnuj Muangsin ^a and Udom Kokpol ^a

^aDepartment of Chemistry, Faculty of Science, Chulalongkorn University, Payathai, Bangkok 10330, Thailand, and ^bDepartment of Physics, Faculty of Science and Technology, Thammasart University, Pathumthani 12121, Thailand
^*Correspondence e-mail: warintho@yahoo.com

(Received 23 August 2009; accepted 28 August 2009; online 9 September 2009)

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.

Related literature

For general background to (+)-(6aS,11aS)-medicarpin, see: Deesamer et al. (2007 ); Hargreaves et al. (1976 ). For a related structure, see: Aree et al. (2003 ).

Experimental

Crystal data

C₁₆H₁₄O₄
M_r = 270.27
Monoclinic, P 2₁
a = 6.6289 (3) Å
b = 8.7963 (4) Å
c = 11.3150 (5) Å
β = 99.4820 (10)°
V = 650.76 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.40 × 0.25 × 0.20 mm

Data collection

Bruker SMART diffractometer
Absorption correction: none
4783 measured reflections
1949 independent reflections
2867 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.093
S = 1.09
1949 reflections
182 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O3ⁱ	0.82	2.07	2.882 (2)	169
Symmetry code: (i) x, y, z+1.

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034485/ng2631sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034485/ng2631Isup2.hkl

checkCIF report

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 CH₂Cl₂crudeextract 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),

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

	Fig. 1. View of the title compound (50% probability displacement ellipsoids)
	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

C₁₆H₁₄O₄	Z = 2
M_r = 270.27	F(000) = 284
Monoclinic, P2₁	D_x = 1.379 Mg m⁻³
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 6.6289 (3) Å	µ = 0.10 mm⁻¹
b = 8.7963 (4) Å	T = 293 K
c = 11.3150 (5) Å	Needle, colourless
β = 99.482 (1)°	0.40 × 0.25 × 0.20 mm
V = 650.76 (5) Å³

Data collection top

Bruker SMART diffractometer	R_int = 0.013
Radiation source: Mo	θ_max = 30.4°, θ_min = 1.8°
ω scans	h = −7→9
4783 measured reflections	k = −12→12
3198 independent reflections	l = −15→13
1949 reflections with I > 2σ(I)

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.034	w = 1/[σ²(F_o²) + (0.0583P)² + 0.0162P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.093	(Δ/σ)_max < 0.001
S = 1.09	Δρ_max = 0.16 e Å⁻³
1949 reflections	Δρ_min = −0.18 e Å⁻³
182 parameters

Crystal data top

C₁₆H₁₄O₄	V = 650.76 (5) Å³
M_r = 270.27	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.6289 (3) Å	µ = 0.10 mm⁻¹
b = 8.7963 (4) Å	T = 293 K
c = 11.3150 (5) Å	0.40 × 0.25 × 0.20 mm
β = 99.482 (1)°

Data collection top

Bruker SMART diffractometer	1949 reflections with I > 2σ(I)
4783 measured reflections	R_int = 0.013
3198 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	1 restraint
wR(F²) = 0.093	H-atom parameters constrained
S = 1.09	Δρ_max = 0.16 e Å⁻³
1949 reflections	Δρ_min = −0.18 e Å⁻³
182 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	0.0057 (2)	0.4390 (2)	0.69102 (16)	0.0414 (4)
H1	−0.1252	0.398	0.6736	0.05*
C2	0.0496 (3)	0.5393 (3)	0.78509 (16)	0.0458 (4)
H2	−0.0512	0.5664	0.8294	0.055*
C3	0.2455 (3)	0.6001 (2)	0.81356 (14)	0.0413 (4)
C4	0.3960 (3)	0.5576 (2)	0.74813 (15)	0.0399 (4)
H4	0.5278	0.5962	0.7678	0.048*
C4A	0.3482 (2)	0.45666 (19)	0.65285 (14)	0.0351 (3)
C6	0.4820 (3)	0.2767 (2)	0.53202 (17)	0.0426 (4)
H6A	0.4918	0.1964	0.5915	0.051*
H6B	0.5928	0.2632	0.4867	0.051*
C6A	0.2800 (2)	0.26311 (19)	0.44829 (15)	0.0365 (3)
H6A1	0.2669	0.1601	0.4149	0.044*
C6B	0.2447 (2)	0.37674 (19)	0.34730 (14)	0.0338 (3)
C7	0.3662 (3)	0.4270 (2)	0.26630 (15)	0.0393 (3)
H7	0.5007	0.3937	0.2723	0.047*
C8	0.2854 (3)	0.5275 (2)	0.17639 (16)	0.0424 (4)
H8	0.367	0.5633	0.123	0.051*
C9	0.0829 (3)	0.5752 (2)	0.16556 (14)	0.0388 (4)
C10	−0.0419 (3)	0.5288 (2)	0.24674 (15)	0.0374 (3)
H10	−0.1764	0.5621	0.2409	0.045*
C10A	0.0455 (2)	0.43038 (19)	0.33679 (13)	0.0332 (3)
C11A	0.0957 (2)	0.29610 (19)	0.51234 (15)	0.0363 (3)
H11A	0.0382	0.2002	0.5358	0.044*
C11B	0.1513 (2)	0.39649 (18)	0.62068 (14)	0.0343 (3)
C12	−0.1997 (3)	0.7026 (3)	0.04448 (19)	0.0579 (5)
H12A	−0.2266	0.7714	−0.0221	0.087*
H12B	−0.2447	0.7474	0.113	0.087*
H12C	−0.2719	0.6091	0.0244	0.087*
O1	0.50439 (17)	0.42138 (16)	0.59175 (11)	0.0436 (3)
O2	−0.05777 (17)	0.37602 (17)	0.42345 (10)	0.0401 (3)
O3	0.0152 (2)	0.67276 (19)	0.07158 (11)	0.0518 (4)
O4	0.2992 (2)	0.7012 (2)	0.90549 (12)	0.0550 (4)
H4A	0.2102	0.7028	0.9479	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0296 (7)	0.0524 (10)	0.0410 (8)	−0.0031 (7)	0.0021 (6)	0.0049 (8)
C2	0.0390 (8)	0.0594 (11)	0.0391 (8)	0.0030 (8)	0.0070 (7)	0.0028 (8)
C3	0.0482 (9)	0.0424 (9)	0.0321 (7)	−0.0012 (7)	0.0026 (6)	0.0048 (7)
C4	0.0368 (7)	0.0448 (9)	0.0372 (7)	−0.0089 (6)	0.0034 (6)	0.0037 (7)
C4A	0.0323 (7)	0.0385 (8)	0.0343 (7)	−0.0031 (6)	0.0045 (6)	0.0059 (6)
C6	0.0361 (7)	0.0445 (10)	0.0460 (9)	0.0054 (7)	0.0030 (7)	0.0002 (7)
C6A	0.0372 (8)	0.0295 (7)	0.0414 (8)	0.0010 (6)	0.0022 (6)	−0.0007 (6)
C6B	0.0347 (7)	0.0306 (7)	0.0354 (7)	0.0000 (6)	0.0039 (6)	−0.0039 (6)
C7	0.0361 (7)	0.0411 (8)	0.0420 (8)	0.0012 (6)	0.0102 (6)	−0.0054 (7)
C8	0.0455 (9)	0.0459 (9)	0.0379 (8)	−0.0007 (7)	0.0130 (7)	−0.0007 (7)
C9	0.0474 (9)	0.0392 (9)	0.0296 (7)	0.0014 (7)	0.0055 (6)	−0.0027 (6)
C10	0.0359 (7)	0.0423 (8)	0.0331 (7)	0.0048 (6)	0.0035 (6)	−0.0023 (6)
C10A	0.0336 (7)	0.0359 (7)	0.0301 (6)	−0.0033 (6)	0.0049 (5)	−0.0032 (6)
C11A	0.0351 (7)	0.0338 (8)	0.0384 (8)	−0.0057 (6)	0.0010 (6)	0.0056 (6)
C11B	0.0310 (6)	0.0360 (8)	0.0342 (7)	−0.0033 (6)	0.0004 (5)	0.0071 (6)
C12	0.0621 (12)	0.0648 (13)	0.0431 (9)	0.0143 (11)	−0.0022 (9)	0.0089 (9)
O1	0.0305 (5)	0.0527 (8)	0.0482 (6)	−0.0086 (5)	0.0087 (4)	−0.0075 (6)
O2	0.0299 (5)	0.0536 (7)	0.0358 (5)	−0.0032 (5)	0.0020 (4)	0.0073 (5)
O3	0.0604 (8)	0.0588 (9)	0.0363 (6)	0.0084 (7)	0.0076 (5)	0.0106 (6)
O4	0.0639 (9)	0.0619 (9)	0.0394 (7)	−0.0071 (7)	0.0088 (6)	−0.0089 (6)

Geometric parameters (Å, º) top

C1—C2	1.376 (3)	C6B—C10A	1.389 (2)
C1—C11B	1.399 (2)	C7—C8	1.387 (3)
C1—H1	0.93	C7—H7	0.93
C2—C3	1.393 (3)	C8—C9	1.393 (2)
C2—H2	0.93	C8—H8	0.93
C3—O4	1.370 (2)	C9—O3	1.382 (2)
C3—C4	1.388 (3)	C9—C10	1.395 (2)
C4—C4A	1.392 (2)	C10—C10A	1.389 (2)
C4—H4	0.93	C10—H10	0.93
C4A—O1	1.372 (2)	C10A—O2	1.3709 (19)
C4A—C11B	1.400 (2)	C11A—O2	1.484 (2)
C6—O1	1.437 (2)	C11A—C11B	1.507 (2)
C6—C6A	1.512 (2)	C11A—H11A	0.98
C6—H6A	0.97	C12—O3	1.431 (3)
C6—H6B	0.97	C12—H12A	0.96
C6A—C6B	1.507 (2)	C12—H12B	0.96
C6A—C11A	1.547 (2)	C12—H12C	0.96
C6A—H6A1	0.98	O4—H4A	0.82
C6B—C7	1.389 (2)

C2—C1—C11B	122.26 (15)	C6B—C7—H7	120.3
C2—C1—H1	118.9	C7—C8—C9	120.45 (16)
C11B—C1—H1	118.9	C7—C8—H8	119.8
C1—C2—C3	119.68 (17)	C9—C8—H8	119.8
C1—C2—H2	120.2	O3—C9—C8	116.15 (16)
C3—C2—H2	120.2	O3—C9—C10	122.38 (15)
O4—C3—C4	117.40 (16)	C8—C9—C10	121.46 (16)
O4—C3—C2	122.73 (17)	C10A—C10—C9	116.39 (15)
C4—C3—C2	119.87 (17)	C10A—C10—H10	121.8
C3—C4—C4A	119.56 (15)	C9—C10—H10	121.8
C3—C4—H4	120.2	O2—C10A—C6B	113.57 (14)
C4A—C4—H4	120.2	O2—C10A—C10	123.03 (14)
O1—C4A—C4	116.13 (14)	C6B—C10A—C10	123.39 (15)
O1—C4A—C11B	122.15 (14)	O2—C11A—C11B	108.81 (14)
C4—C4A—C11B	121.72 (14)	O2—C11A—C6A	106.09 (13)
O1—C6—C6A	112.14 (14)	C11B—C11A—C6A	112.62 (13)
O1—C6—H6A	109.2	O2—C11A—H11A	109.7
C6A—C6—H6A	109.2	C11B—C11A—H11A	109.7
O1—C6—H6B	109.2	C6A—C11A—H11A	109.7
C6A—C6—H6B	109.2	C1—C11B—C4A	116.87 (15)
H6A—C6—H6B	107.9	C1—C11B—C11A	121.33 (14)
C6B—C6A—C6	115.68 (14)	C4A—C11B—C11A	121.74 (14)
C6B—C6A—C11A	101.24 (12)	O3—C12—H12A	109.5
C6—C6A—C11A	112.20 (14)	O3—C12—H12B	109.5
C6B—C6A—H6A1	109.1	H12A—C12—H12B	109.5
C6—C6A—H6A1	109.1	O3—C12—H12C	109.5
C11A—C6A—H6A1	109.1	H12A—C12—H12C	109.5
C7—C6B—C10A	118.82 (15)	H12B—C12—H12C	109.5
C7—C6B—C6A	132.64 (14)	C4A—O1—C6	114.15 (13)
C10A—C6B—C6A	108.46 (13)	C10A—O2—C11A	106.43 (12)
C8—C7—C6B	119.42 (15)	C9—O3—C12	117.65 (15)
C8—C7—H7	120.3	C3—O4—H4A	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O3ⁱ	0.82	2.07	2.882 (2)	169

Symmetry code: (i) x, y, z+1.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄O₄
M_r	270.27
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	6.6289 (3), 8.7963 (4), 11.3150 (5)
β (°)	99.482 (1)
V (Å³)	650.76 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.40 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4783, 3198, 1949
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.712

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.093, 1.09
No. of reflections	1949
No. of parameters	182
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.18

Computer programs: SMART (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O3ⁱ	0.82	2.07	2.882 (2)	169.2

Symmetry code: (i) x, y, z+1.

Acknowledgements

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

References

Aree, T., Tip-pyang, S., Seesukphronrarak, S. & Chaichit, N. (2003). Acta Cryst. E59, o363–o365. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2006). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Deesamer, S., Kokpola, U., Chavasiria, W., Douillardb, S., Peyrotb, V., Vidalc, N. & Combesc, S. (2007). Tetrahedron, 63, 12986–12993. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Hargreaves, J. A., Mansfield, J. W. & Coxon, D. T. (1976). Nature (London), 262, 318–319. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S1600536809034485

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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