3-Hydr-oxy-3a,6,8c-trimethyl-perhydro-oxireno[2',3':7,8]naphtho[1,2-b]furan-7(2H)-one.

The title compound, C(15)H(22)O(4), consists of two trans-fused six-membered rings and a trans-fused five-membered γ-lactone. The ep-oxy and hydroxyl groups are α-oriented. The cyclo-hexane rings adopt half-chair and chair conformations and the lactone ring is in an envelope conformation. The mol-ecular structure is stabilized by one O-H⋯O and three C-H⋯O intra-molecular hydrogen bonds.

Related literature

For background to sesquiterpene lactones, see: Fraga (2008 ▶). For their biological activity, see: Pillay et al. (2007 ▶); Ohno et al. (2005 ▶); Lindenmeyer et al. (2006 ▶). For synthetic details, see: Villar et al. (1983 ▶); González, et al. (1982 ▶). For a related structure, see: Rychlewska et al. (1982 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C15H22O4

M = 266.33

Monoclinic,

a = 8.251 (3) Å

b = 7.239 (2) Å

c = 11.434 (2) Å

β = 94.201 (5)°

V = 681.1 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 292 K

0.20 × 0.09 × 0.08 mm

Data collection

Nonius KappaCCD area-detector diffractometer

Absorption correction: none

6696 measured reflections

1601 independent reflections

1495 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.108

S = 1.13

1601 reflections

179 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.17 e Å−3

Δρmin = −0.15 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); 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 datablocks global, I. DOI: 10.1107/S1600536809025124/pv2169sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025124/pv2169Isup2.hkl

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

C15H22O4	F(000) = 288
Mr = 266.33	Dx = 1.299 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2yb	Cell parameters from 1601 reflections
a = 8.251 (3) Å	θ = 2.4–27.1°
b = 7.239 (2) Å	µ = 0.09 mm−1
c = 11.434 (2) Å	T = 292 K
β = 94.201 (5)°	Block, colourless
V = 681.1 (3) Å3	0.20 × 0.09 × 0.08 mm
Z = 2

Nonius KappaCCD area-detector diffractometer	1495 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.042
graphite	θmax = 27.1°, θmin = 2.5°
φ scans, and ω scans with κ offsets	h = −8→10
6696 measured reflections	k = −9→9
1601 independent reflections	l = −14→14

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ2(Fo2) + (0.0654P)2 + 0.0443P] where P = (Fo2 + 2Fc2)/3
1601 reflections	(Δ/σ)max < 0.001
179 parameters	Δρmax = 0.17 e Å−3
1 restraint	Δρmin = −0.15 e Å−3

Experimental. Melting points were determined on a Kofler-type apparatus and are uncorrected. The IR spectra were recorded on a Perkin-Elmer Spectrum BX spectrophotometer with KBr as support. The 1H-NMR spectra were obtained with a Brüker Advance DPX-400 at 400 MHz. The MS spectra were recorded on a VG AUTOSPEC FISON instrument. In the purification of the intermediates and final product column chromatography was carried out using Merck silica gel 0.065–0.2 mm. Melting point 473–475 K. IR cm-1: 3529 (O—H), 1769 (γ-lactone). 1H-NMR, δ (CDCl3): 3.96 (1H, dd, J=9.7 and 8.5 Hz, H6), 3.21 (1H, bs, H1), 3.03 (1H, bs, H3), 1.49 (3H, s, H15), 1.24 (3H, d, J= 6.8 Hz, H13), 1.21 (3H, s, H14). MS (m/z): 266.15 (M+, C15H22O4), 248.14 (M+– H2O).

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
O1	0.6128 (2)	0.3084 (3)	0.41480 (13)	0.0546 (5)
O2	0.51059 (16)	0.2973 (2)	0.58981 (11)	0.0384 (4)
O3	0.4263 (2)	0.0404 (3)	0.90667 (14)	0.0489 (4)
O4	0.0735 (3)	−0.0003 (3)	0.84929 (18)	0.0662 (6)
H4	0.164 (5)	−0.035 (7)	0.855 (4)	0.093 (15)*
C1	0.0892 (3)	0.1905 (4)	0.8793 (2)	0.0509 (6)
H1	−0.0187	0.2346	0.8966	0.061*
C2	0.2005 (3)	0.2157 (5)	0.98982 (19)	0.0541 (6)
H2A	0.179	0.3351	1.024	0.065*
H2B	0.176	0.1214	1.0462	0.065*
C3	0.3763 (3)	0.2043 (4)	0.96754 (17)	0.0445 (5)
H3	0.4521	0.2468	1.0319	0.053*
C4	0.4356 (2)	0.2197 (3)	0.84932 (16)	0.0356 (4)
C5	0.3118 (2)	0.2328 (3)	0.74257 (15)	0.0303 (4)
H5	0.2925	0.1061	0.7149	0.036*
C6	0.3554 (2)	0.3442 (3)	0.63683 (15)	0.0316 (4)
H6	0.3543	0.4761	0.6561	0.038*
C7	0.2322 (2)	0.3066 (3)	0.53335 (16)	0.0364 (4)
H7	0.2211	0.1723	0.5256	0.044*
C8	0.0672 (3)	0.3830 (4)	0.55853 (19)	0.0475 (6)
H8A	−0.0119	0.3553	0.4939	0.057*
H8B	0.0733	0.516	0.5679	0.057*
C9	0.0161 (2)	0.2934 (4)	0.67131 (19)	0.0490 (6)
H9A	−0.0068	0.1639	0.6561	0.059*
H9B	−0.0837	0.351	0.6926	0.059*
C10	0.1444 (2)	0.3084 (3)	0.77649 (17)	0.0385 (5)
C11	0.3227 (3)	0.3750 (3)	0.43019 (17)	0.0395 (5)
H11	0.3129	0.5097	0.4256	0.047*
C12	0.4968 (3)	0.3260 (3)	0.47164 (16)	0.0382 (4)
C13	0.2728 (4)	0.2936 (5)	0.31047 (19)	0.0603 (7)
H13A	0.3448	0.3376	0.2544	0.09*
H13B	0.1635	0.3305	0.2868	0.09*
H13C	0.2785	0.1613	0.3146	0.09*
C14	0.1588 (3)	0.5107 (4)	0.8180 (2)	0.0560 (6)
H14A	0.0679	0.5408	0.8623	0.084*
H14B	0.1595	0.5908	0.7512	0.084*
H14C	0.2578	0.5264	0.8665	0.084*
C15	0.6070 (3)	0.2836 (5)	0.83987 (19)	0.0543 (7)
H15A	0.6664	0.273	0.915	0.081*
H15B	0.6066	0.4102	0.8148	0.081*
H15C	0.6578	0.2086	0.7838	0.081*

	U11	U22	U33	U12	U13	U23
O1	0.0602 (10)	0.0587 (10)	0.0481 (8)	0.0041 (9)	0.0264 (7)	0.0041 (9)
O2	0.0331 (6)	0.0470 (8)	0.0366 (7)	0.0030 (7)	0.0118 (5)	0.0026 (7)
O3	0.0554 (9)	0.0485 (10)	0.0431 (8)	0.0042 (8)	0.0058 (6)	0.0103 (7)
O4	0.0588 (12)	0.0673 (13)	0.0729 (13)	−0.0278 (11)	0.0077 (9)	0.0140 (11)
C1	0.0335 (10)	0.0708 (18)	0.0504 (12)	−0.0031 (12)	0.0166 (9)	0.0062 (12)
C2	0.0484 (12)	0.0761 (18)	0.0400 (10)	−0.0032 (14)	0.0186 (9)	0.0033 (12)
C3	0.0437 (11)	0.0569 (15)	0.0332 (9)	−0.0071 (11)	0.0051 (8)	0.0002 (10)
C4	0.0323 (9)	0.0401 (11)	0.0350 (9)	0.0002 (9)	0.0069 (7)	0.0001 (9)
C5	0.0261 (8)	0.0312 (9)	0.0342 (9)	−0.0001 (8)	0.0076 (6)	−0.0023 (8)
C6	0.0293 (8)	0.0328 (10)	0.0336 (9)	0.0012 (8)	0.0080 (7)	−0.0007 (7)
C7	0.0381 (10)	0.0341 (10)	0.0374 (9)	0.0014 (9)	0.0042 (7)	0.0025 (9)
C8	0.0364 (10)	0.0569 (15)	0.0489 (11)	0.0073 (10)	−0.0006 (8)	0.0046 (11)
C9	0.0271 (8)	0.0639 (15)	0.0565 (12)	0.0041 (10)	0.0061 (8)	0.0066 (12)
C10	0.0286 (8)	0.0460 (12)	0.0422 (9)	0.0023 (9)	0.0112 (7)	0.0010 (10)
C11	0.0495 (11)	0.0351 (10)	0.0341 (9)	−0.0003 (9)	0.0052 (8)	0.0014 (8)
C12	0.0457 (10)	0.0329 (10)	0.0374 (10)	−0.0004 (9)	0.0127 (8)	0.0014 (8)
C13	0.0753 (16)	0.0665 (17)	0.0382 (11)	0.0005 (15)	−0.0017 (10)	−0.0045 (13)
C14	0.0557 (14)	0.0527 (15)	0.0622 (15)	0.0166 (12)	0.0215 (11)	−0.0093 (12)
C15	0.0320 (9)	0.089 (2)	0.0418 (10)	−0.0093 (12)	0.0040 (8)	0.0017 (13)

O1—C12	1.202 (2)	C7—C8	1.516 (3)
O2—C12	1.364 (2)	C7—C11	1.524 (3)
O2—C6	1.464 (2)	C7—H7	0.98
O3—C3	1.451 (3)	C8—C9	1.530 (3)
O3—C4	1.459 (3)	C8—H8A	0.97
O4—C1	1.427 (4)	C8—H8B	0.97
O4—H4	0.78 (4)	C9—C10	1.547 (3)
C1—C2	1.517 (3)	C9—H9A	0.97
C1—C10	1.548 (3)	C9—H9B	0.97
C1—H1	0.98	C10—C14	1.541 (4)
C2—C3	1.493 (3)	C11—C13	1.519 (3)
C2—H2A	0.97	C11—C12	1.521 (3)
C2—H2B	0.97	C11—H11	0.98
C3—C4	1.475 (3)	C13—H13A	0.96
C3—H3	0.98	C13—H13B	0.96
C4—C15	1.500 (3)	C13—H13C	0.96
C4—C5	1.536 (3)	C14—H14A	0.96
C5—C6	1.518 (2)	C14—H14B	0.96
C5—C10	1.561 (2)	C14—H14C	0.96
C5—H5	0.98	C15—H15A	0.96
C6—C7	1.527 (3)	C15—H15B	0.96
C6—H6	0.98	C15—H15C	0.96
C12—O2—C6	108.47 (14)	C7—C8—C9	108.19 (19)
C3—O3—C4	60.93 (13)	C7—C8—H8A	110.1
C1—O4—H4	103 (4)	C9—C8—H8A	110.1
O4—C1—C2	110.8 (2)	C7—C8—H8B	110.1
O4—C1—C10	112.2 (2)	C9—C8—H8B	110.1
C2—C1—C10	111.9 (2)	H8A—C8—H8B	108.4
O4—C1—H1	107.2	C8—C9—C10	114.25 (18)
C2—C1—H1	107.2	C8—C9—H9A	108.7
C10—C1—H1	107.2	C10—C9—H9A	108.7
C3—C2—C1	112.77 (17)	C8—C9—H9B	108.7
C3—C2—H2A	109	C10—C9—H9B	108.7
C1—C2—H2A	109	H9A—C9—H9B	107.6
C3—C2—H2B	109	C14—C10—C9	109.8 (2)
C1—C2—H2B	109	C14—C10—C1	108.05 (19)
H2A—C2—H2B	107.8	C9—C10—C1	109.22 (19)
O3—C3—C4	59.79 (13)	C14—C10—C5	111.13 (18)
O3—C3—C2	116.2 (2)	C9—C10—C5	110.48 (16)
C4—C3—C2	122.93 (18)	C1—C10—C5	108.08 (18)
O3—C3—H3	115.4	C13—C11—C12	112.21 (19)
C4—C3—H3	115.4	C13—C11—C7	117.1 (2)
C2—C3—H3	115.4	C12—C11—C7	100.87 (15)
O3—C4—C3	59.28 (14)	C13—C11—H11	108.7
O3—C4—C15	112.81 (18)	C12—C11—H11	108.7
C3—C4—C15	117.85 (17)	C7—C11—H11	108.7
O3—C4—C5	111.03 (17)	O1—C12—O2	120.52 (19)
C3—C4—C5	119.16 (16)	O1—C12—C11	128.83 (18)
C15—C4—C5	119.95 (17)	O2—C12—C11	110.63 (15)
C6—C5—C4	118.90 (15)	C11—C13—H13A	109.5
C6—C5—C10	106.09 (15)	C11—C13—H13B	109.5
C4—C5—C10	111.90 (15)	H13A—C13—H13B	109.5
C6—C5—H5	106.4	C11—C13—H13C	109.5
C4—C5—H5	106.4	H13A—C13—H13C	109.5
C10—C5—H5	106.4	H13B—C13—H13C	109.5
O2—C6—C5	115.68 (15)	C10—C14—H14A	109.5
O2—C6—C7	102.98 (14)	C10—C14—H14B	109.5
C5—C6—C7	109.82 (16)	H14A—C14—H14B	109.5
O2—C6—H6	109.4	C10—C14—H14C	109.5
C5—C6—H6	109.4	H14A—C14—H14C	109.5
C7—C6—H6	109.4	H14B—C14—H14C	109.5
C8—C7—C11	121.77 (19)	C4—C15—H15A	109.5
C8—C7—C6	110.13 (17)	C4—C15—H15B	109.5
C11—C7—C6	101.85 (16)	H15A—C15—H15B	109.5
C8—C7—H7	107.4	C4—C15—H15C	109.5
C11—C7—H7	107.4	H15A—C15—H15C	109.5
C6—C7—H7	107.4	H15B—C15—H15C	109.5
O4—C1—C2—C3	79.3 (3)	C11—C7—C8—C9	−176.7 (2)
C10—C1—C2—C3	−46.7 (3)	C6—C7—C8—C9	−57.7 (3)
C4—O3—C3—C2	114.5 (2)	C7—C8—C9—C10	52.5 (3)
C1—C2—C3—O3	−53.5 (3)	C8—C9—C10—C14	69.4 (3)
C1—C2—C3—C4	16.1 (4)	C8—C9—C10—C1	−172.3 (2)
C3—O3—C4—C15	109.9 (2)	C8—C9—C10—C5	−53.5 (3)
C3—O3—C4—C5	−112.26 (18)	O4—C1—C10—C14	−179.6 (2)
C2—C3—C4—O3	−103.4 (3)	C2—C1—C10—C14	−54.3 (3)
O3—C3—C4—C15	−101.3 (2)	O4—C1—C10—C9	61.0 (3)
C2—C3—C4—C15	155.3 (3)	C2—C1—C10—C9	−173.8 (2)
O3—C3—C4—C5	98.4 (2)	O4—C1—C10—C5	−59.3 (2)
C2—C3—C4—C5	−4.9 (4)	C2—C1—C10—C5	66.0 (3)
O3—C4—C5—C6	−146.38 (16)	C6—C5—C10—C14	−65.2 (2)
C3—C4—C5—C6	148.0 (2)	C4—C5—C10—C14	66.0 (2)
C15—C4—C5—C6	−11.9 (3)	C6—C5—C10—C9	57.0 (2)
O3—C4—C5—C10	89.3 (2)	C4—C5—C10—C9	−171.85 (19)
C3—C4—C5—C10	23.7 (3)	C6—C5—C10—C1	176.44 (18)
C15—C4—C5—C10	−136.2 (2)	C4—C5—C10—C1	−52.4 (2)
C12—O2—C6—C5	148.07 (17)	C8—C7—C11—C13	−81.2 (3)
C12—O2—C6—C7	28.3 (2)	C6—C7—C11—C13	155.8 (2)
C4—C5—C6—O2	52.5 (2)	C8—C7—C11—C12	156.7 (2)
C10—C5—C6—O2	179.57 (16)	C6—C7—C11—C12	33.8 (2)
C4—C5—C6—C7	168.51 (17)	C6—O2—C12—O1	175.0 (2)
C10—C5—C6—C7	−64.4 (2)	C6—O2—C12—C11	−6.3 (2)
O2—C6—C7—C8	−169.05 (17)	C13—C11—C12—O1	34.9 (4)
C5—C6—C7—C8	67.2 (2)	C7—C11—C12—O1	160.3 (3)
O2—C6—C7—C11	−38.5 (2)	C13—C11—C12—O2	−143.7 (2)
C5—C6—C7—C11	−162.29 (16)	C7—C11—C12—O2	−18.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3	0.79 (4)	2.27 (4)	2.952 (3)	146 (5)
C9—H9A···O4	0.97	2.55	2.958 (3)	105
C5—H5···O4	0.98	2.57	2.925 (3)	101
C15—H15C···O2	0.96	2.53	2.913 (3)	104

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O3	0.79 (4)	2.27 (4)	2.952 (3)	146 (5)
C9—H9A⋯O4	0.97	2.55	2.958 (3)	105
C5—H5⋯O4	0.98	2.57	2.925 (3)	101
C15—H15C⋯O2	0.96	2.53	2.913 (3)	104