9β-Hy-droxy-6,9-dimethyl-3-methyl-ene-3a,4,8,9,9a,9b-hexa-hydro-azuleno[4,5-b]furan-2(3H)-one.

The title compound, C(15)H(18)O(3), was synthesized from 9α-hy-droxy-parthenolide (9α-hy-droxy-4,8-dimethyl-12-methylen-3,14-dioxa-tricyclo-[9.3.0.0(2,4)]tetra-dec-7-en-13-one), which was isolated from the chloro-form extract of the aerial parts of Anvillea radiata. The seven-membered ring of the title compound shows a chair conformation, while the five-membered rings exibit different conformations, viz a twisted one for the lactone ring and an envelope conformation for the other five-membered ring with the C atom closest to the hydroxy group forming the flap. In the crystal, O-H⋯O hydrogen bonds connect mol-ecules into dimers that are inter-connected by C-H⋯O inter-actions, producing supramolecular chains along the b axis.

Related literature

For background to the medicinal uses of the plant Anvillea radiata, see: Abdel Sattar et al. (1996 ▶); Bellakhdar (1997 ▶); El Hassany et al. (2004 ▶); Qureshi et al. (1990 ▶). For the reactivity of this sesquiterpene, see: El Haib et al. (2011 ▶) For ring puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C15H18O3

M = 246.29

Monoclinic,

a = 15.6732 (9) Å

b = 7.4208 (4) Å

c = 11.0544 (6) Å

β = 103.169 (6)°

V = 1251.90 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 180 K

0.42 × 0.19 × 0.12 mm

Data collection

Agilent Xcalibur Eos Gemini Ultra diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T min = 0.631, T max = 1.000

13492 measured reflections

1378 independent reflections

1313 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.080

S = 1.05

1378 reflections

166 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.15 e Å−3

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812000165/im2349sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812000165/im2349Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812000165/im2349Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C15H18O3	F(000) = 528
Mr = 246.29	Dx = 1.307 Mg m−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 9785 reflections
a = 15.6732 (9) Å	θ = 3–26.4°
b = 7.4208 (4) Å	µ = 0.09 mm−1
c = 11.0544 (6) Å	T = 180 K
β = 103.169 (6)°	Box, pale yellow
V = 1251.90 (12) Å3	0.42 × 0.19 × 0.12 mm
Z = 4

Agilent Xcalibur Eos Gemini Ultra diffractometer	1378 independent reflections
Radiation source: fine-focus sealed tube	1313 reflections with I > 2σ(I)
graphite	Rint = 0.029
Detector resolution: 8.2632 pixels mm-1	θmax = 26.4°, θmin = 3.1°
ω scans	h = −19→19
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −9→9
Tmin = 0.631, Tmax = 1.000	l = −13→13
13492 measured reflections

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0581P)2 + 0.1945P] where P = (Fo2 + 2Fc2)/3
1378 reflections	(Δ/σ)max < 0.001
166 parameters	Δρmax = 0.19 e Å−3
1 restraint	Δρmin = −0.15 e Å−3

Experimental. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. CrysAlisPro (Agilent Technologies, 2010)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

	x	y	z	Uiso*/Ueq
C1	0.80721 (11)	0.4633 (2)	0.61618 (14)	0.0267 (3)
C2	0.87339 (12)	0.4573 (3)	0.55907 (15)	0.0380 (4)
H2	0.8666	0.4746	0.4741	0.046*
C3	0.95947 (12)	0.4201 (4)	0.64549 (17)	0.0455 (5)
H3A	1.0049	0.4976	0.6278	0.055*
H3B	0.9766	0.2953	0.6399	0.055*
C4	0.94229 (10)	0.4614 (3)	0.77340 (14)	0.0322 (4)
C5	0.84280 (10)	0.4259 (2)	0.75363 (14)	0.0246 (3)
H5	0.8353	0.2968	0.7666	0.030*
C6	0.79591 (9)	0.5247 (2)	0.83742 (14)	0.0233 (3)
H6	0.7950	0.6540	0.8192	0.028*
C7	0.70300 (10)	0.4572 (2)	0.82786 (14)	0.0265 (3)
H7	0.7016	0.3276	0.8106	0.032*
C8	0.63569 (11)	0.5483 (3)	0.72710 (16)	0.0338 (4)
H8A	0.5782	0.5047	0.7319	0.041*
H8B	0.6372	0.6766	0.7443	0.041*
C9	0.64585 (11)	0.5222 (3)	0.59733 (16)	0.0323 (4)
H9	0.5935	0.5305	0.5378	0.039*
C10	0.71551 (11)	0.4891 (2)	0.54969 (14)	0.0287 (4)
C11	0.69280 (10)	0.4841 (2)	0.95746 (15)	0.0283 (3)
C12	0.78211 (11)	0.4836 (2)	1.03860 (15)	0.0290 (3)
C13	0.62238 (13)	0.5135 (3)	1.00137 (19)	0.0401 (5)
H13A	0.6280	0.5349	1.0857	0.048*
H13B	0.5672	0.5129	0.9479	0.048*
C14	0.70133 (13)	0.4837 (3)	0.41040 (15)	0.0402 (4)
H14A	0.6403	0.5011	0.3734	0.060*
H14B	0.7198	0.3690	0.3855	0.060*
H14C	0.7348	0.5777	0.3835	0.060*
C15	0.96829 (12)	0.6516 (3)	0.81170 (19)	0.0416 (5)
H15A	0.9542	0.6767	0.8901	0.062*
H15B	0.9371	0.7335	0.7501	0.062*
H15C	1.0302	0.6660	0.8194	0.062*
O1	0.80505 (9)	0.4767 (2)	1.14968 (11)	0.0415 (3)
O2	0.84070 (7)	0.49325 (18)	0.96669 (9)	0.0290 (3)
O3	0.98840 (8)	0.3361 (2)	0.86299 (13)	0.0437 (4)
H3	1.0346	0.3813	0.9005	0.065*

	U11	U22	U33	U12	U13	U23
C1	0.0301 (8)	0.0277 (8)	0.0211 (7)	0.0032 (7)	0.0037 (6)	−0.0003 (7)
C2	0.0369 (9)	0.0543 (12)	0.0231 (7)	0.0066 (10)	0.0078 (7)	0.0013 (9)
C3	0.0317 (9)	0.0765 (16)	0.0308 (9)	0.0111 (10)	0.0126 (7)	0.0002 (9)
C4	0.0201 (7)	0.0513 (11)	0.0253 (7)	0.0084 (8)	0.0054 (6)	0.0037 (8)
C5	0.0222 (7)	0.0281 (8)	0.0230 (7)	0.0048 (6)	0.0039 (5)	0.0012 (6)
C6	0.0211 (7)	0.0267 (8)	0.0215 (7)	0.0020 (6)	0.0038 (5)	0.0009 (6)
C7	0.0219 (7)	0.0281 (8)	0.0299 (8)	0.0012 (6)	0.0066 (6)	0.0011 (7)
C8	0.0204 (7)	0.0410 (10)	0.0386 (10)	0.0043 (7)	0.0037 (7)	0.0056 (8)
C9	0.0241 (8)	0.0351 (10)	0.0325 (8)	−0.0005 (7)	−0.0044 (6)	0.0052 (7)
C10	0.0316 (8)	0.0247 (8)	0.0258 (7)	0.0001 (7)	−0.0018 (6)	0.0015 (7)
C11	0.0298 (8)	0.0238 (8)	0.0337 (8)	0.0013 (7)	0.0122 (6)	0.0021 (7)
C12	0.0336 (8)	0.0276 (8)	0.0282 (8)	0.0031 (8)	0.0122 (6)	−0.0002 (7)
C13	0.0361 (9)	0.0428 (11)	0.0471 (10)	0.0010 (8)	0.0218 (8)	0.0011 (9)
C14	0.0467 (10)	0.0422 (11)	0.0261 (8)	0.0043 (10)	−0.0030 (7)	0.0002 (8)
C15	0.0245 (8)	0.0556 (12)	0.0437 (10)	−0.0066 (8)	0.0054 (7)	0.0022 (10)
O1	0.0481 (7)	0.0523 (8)	0.0255 (6)	0.0011 (7)	0.0114 (5)	−0.0005 (6)
O2	0.0244 (5)	0.0407 (7)	0.0218 (5)	0.0026 (5)	0.0049 (4)	−0.0002 (5)
O3	0.0232 (6)	0.0660 (10)	0.0394 (7)	0.0125 (6)	0.0021 (5)	0.0152 (7)

C1—C2	1.332 (2)	C8—C9	1.492 (3)
C1—C10	1.470 (2)	C8—H8A	0.9700
C1—C5	1.520 (2)	C8—H8B	0.9700
C2—C3	1.491 (2)	C9—C10	1.339 (3)
C2—H2	0.9300	C9—H9	0.9300
C3—C4	1.530 (2)	C10—C14	1.505 (2)
C3—H3A	0.9700	C11—C13	1.321 (2)
C3—H3B	0.9700	C11—C12	1.481 (2)
C4—O3	1.429 (2)	C12—O1	1.199 (2)
C4—C15	1.503 (3)	C12—O2	1.3464 (19)
C4—C5	1.547 (2)	C13—H13A	0.9300
C5—C6	1.498 (2)	C13—H13B	0.9300
C5—H5	0.9800	C14—H14A	0.9600
C6—O2	1.4602 (18)	C14—H14B	0.9600
C6—C7	1.520 (2)	C14—H14C	0.9600
C6—H6	0.9800	C15—H15A	0.9600
C7—C11	1.491 (2)	C15—H15B	0.9600
C7—C8	1.508 (2)	C15—H15C	0.9600
C7—H7	0.9800	O3—H3	0.8200
C2—C1—C10	123.05 (14)	C9—C8—C7	116.23 (15)
C2—C1—C5	108.64 (14)	C9—C8—H8A	108.2
C10—C1—C5	128.16 (14)	C7—C8—H8A	108.2
C1—C2—C3	113.02 (14)	C9—C8—H8B	108.2
C1—C2—H2	123.5	C7—C8—H8B	108.2
C3—C2—H2	123.5	H8A—C8—H8B	107.4
C2—C3—C4	103.37 (14)	C10—C9—C8	132.66 (15)
C2—C3—H3A	111.1	C10—C9—H9	113.7
C4—C3—H3A	111.1	C8—C9—H9	113.7
C2—C3—H3B	111.1	C9—C10—C1	128.26 (14)
C4—C3—H3B	111.1	C9—C10—C14	117.63 (15)
H3A—C3—H3B	109.1	C1—C10—C14	114.06 (15)
O3—C4—C15	110.74 (15)	C13—C11—C12	122.10 (16)
O3—C4—C3	110.03 (16)	C13—C11—C7	131.05 (16)
C15—C4—C3	110.80 (17)	C12—C11—C7	106.76 (13)
O3—C4—C5	108.76 (15)	O1—C12—O2	121.41 (15)
C15—C4—C5	113.55 (15)	O1—C12—C11	129.93 (15)
C3—C4—C5	102.67 (13)	O2—C12—C11	108.66 (13)
C6—C5—C1	114.13 (13)	C11—C13—H13A	120.0
C6—C5—C4	116.75 (13)	C11—C13—H13B	120.0
C1—C5—C4	103.81 (12)	H13A—C13—H13B	120.0
C6—C5—H5	107.2	C10—C14—H14A	109.5
C1—C5—H5	107.2	C10—C14—H14B	109.5
C4—C5—H5	107.2	H14A—C14—H14B	109.5
O2—C6—C5	109.43 (12)	C10—C14—H14C	109.5
O2—C6—C7	104.76 (11)	H14A—C14—H14C	109.5
C5—C6—C7	113.14 (13)	H14B—C14—H14C	109.5
O2—C6—H6	109.8	C4—C15—H15A	109.5
C5—C6—H6	109.8	C4—C15—H15B	109.5
C7—C6—H6	109.8	H15A—C15—H15B	109.5
C11—C7—C8	116.08 (14)	C4—C15—H15C	109.5
C11—C7—C6	101.53 (12)	H15A—C15—H15C	109.5
C8—C7—C6	113.67 (14)	H15B—C15—H15C	109.5
C11—C7—H7	108.4	C12—O2—C6	110.23 (12)
C8—C7—H7	108.4	C4—O3—H3	109.5
C6—C7—H7	108.4

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2i	0.82	2.31	3.128 (2)	171
C8—H8B···O1ii	0.97	2.58	3.500 (2)	158
C7—H7···O1iii	0.98	2.65	3.579 (2)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2i	0.82	2.31	3.128 (2)	171
C8—H8B⋯O1ii	0.97	2.58	3.500 (2)	158
C7—H7⋯O1iii	0.98	2.65	3.579 (2)	159

Symmetry codes: (i) ; (ii) ; (iii) .