Crystal structure of (1R,3S,8R,11R)-11-acetyl-3,7,7-trimethyl-10-oxatri-cyclo-[6.4.0.0(1,3)]dodecan-9-one.

The title compound, C16H24O3, is built up from three fused rings, a six-membered, a seven-membered and a three-membered ring. The absolute configuration of the title compound was determined as (1R,3S,8R,11R) based on the synthetic pathway. The six-membered ring has an half-chair conformation whereas the seven-membered ring displays a boat conformation. In the cyrstal, C-H⋯O hydrogen bonds build up a two-dimensional network parallel to (0 0 1). The crystal studied was an inversion twin with a minor twin component of 34%.

Related literature

For biological activities of terpenic lactones, see: Hall et al. (1987 ▸); Ohnishi et al. (1997 ▸); Ghosh & Karin (2002 ▸); Bremner & Heinrich (2002 ▸); Francois et al. (1996 ▸); Rabe et al. (2002 ▸); Calera et al. (1995 ▸). For the synthesis, see: Bimoussa et al. (2014 ▸). For the ring puckering parameters, see: Boessenkool & Boyens (1980 ▸). For the absolute configuration, see: Parsons et al. (2013 ▸); Hooft et al. (2008 ▸). For the refinement of twined crystals, see: Cooper et al. (2002 ▸).

Experimental

Crystal data

C16H24O3

M = 264.35

Monoclinic,

a = 6.4443 (6) Å

b = 8.4437 (7) Å

c = 13.7083 (12) Å

β = 98.654 (9)°

V = 737.43 (11) Å3

Z = 2

Mo Kα radiation

μ = 0.08 mm−1

T = 180 K

0.52 × 0.45 × 0.25 mm

Data collection

Agilent Xcalibur (Eos, Gemini ultra) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014 ▸). T min = 0.717, T max = 1.000

7878 measured reflections

7878 independent reflections

7173 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.061

wR(F 2) = 0.141

S = 1.05

7878 reflections

177 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.34 e Å−3

Data collection: CrysAlis PRO (Agilent, 2014 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▸) and ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL2013.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015022847/xu5880sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015022847/xu5880Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015022847/xu5880Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015022847/xu5880fig1.tif

Mol­ecular view of the title compound with the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circle of arbitrary radii.

Click here for additional data file.

x y z x y z . DOI: 10.1107/S2056989015022847/xu5880fig2.tif

Packing view showing the C—H⋯O hydrogen bonds building a two-dimensional network. H bonds are shown as dashed lines. [Symmetry codes: (i) x + 1, y, z; (ii) −x + 1, y + , −z + 1].

CCDC reference: 1439412

Additional supporting information: crystallographic information; 3D view; checkCIF report

C16H24O3	F(000) = 288
Mr = 264.35	Dx = 1.191 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 6.4443 (6) Å	Cell parameters from 2697 reflections
b = 8.4437 (7) Å	θ = 4.0–28.4°
c = 13.7083 (12) Å	µ = 0.08 mm−1
β = 98.654 (9)°	T = 180 K
V = 737.43 (11) Å3	Box, colourless
Z = 2	0.52 × 0.45 × 0.25 mm

Agilent Xcalibur (Eos, Gemini ultra) diffractometer	7878 independent reflections
Radiation source: Enhance (Mo) X-ray Source	7173 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
Detector resolution: 16.1978 pixels mm-1	θmax = 26.4°, θmin = 3.0°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014).	k = −10→10
Tmin = 0.717, Tmax = 1.000	l = −17→16
7878 measured reflections

Refinement on F2	1 restraint
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.061	H-atom parameters constrained
wR(F2) = 0.141	w = 1/[σ2(Fo2) + (0.0238P)2 + 0.9242P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
7878 reflections	Δρmax = 0.31 e Å−3
177 parameters	Δρmin = −0.34 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.2887 (8)	0.3804 (6)	0.2813 (4)	0.0237 (11)
C2	0.3418 (9)	0.2072 (6)	0.2798 (4)	0.0297 (12)
H2A	0.2894	0.1378	0.3289	0.036*
H2B	0.4811	0.1776	0.2634	0.036*
C3	0.1834 (8)	0.2745 (7)	0.1985 (4)	0.0274 (12)
C4	0.2531 (10)	0.2989 (7)	0.0992 (4)	0.0359 (14)
H4A	0.2061	0.2079	0.0559	0.043*
H4B	0.4084	0.3023	0.1078	0.043*
C5	0.1648 (11)	0.4526 (8)	0.0492 (4)	0.0482 (17)
H5A	0.0218	0.4315	0.0140	0.058*
H5B	0.2534	0.4840	−0.0006	0.058*
C6	0.1541 (10)	0.5920 (7)	0.1208 (4)	0.0402 (15)
H6A	0.1000	0.6852	0.0811	0.048*
H6B	0.0487	0.5650	0.1637	0.048*
C7	0.3540 (9)	0.6425 (7)	0.1873 (4)	0.0378 (14)
C8	0.4454 (8)	0.5023 (6)	0.2584 (4)	0.0278 (13)
H8	0.5466	0.4443	0.2228	0.033*
C9	0.5737 (8)	0.5692 (7)	0.3498 (4)	0.0319 (13)
C10	0.3256 (8)	0.4700 (7)	0.4541 (4)	0.0266 (12)
H10	0.3797	0.3666	0.4830	0.032*
C11	0.1686 (8)	0.4366 (6)	0.3621 (3)	0.0234 (11)
H11A	0.0888	0.5340	0.3408	0.028*
H11B	0.0680	0.3541	0.3762	0.028*
C12	−0.0452 (8)	0.2292 (7)	0.1912 (4)	0.0371 (15)
H12A	−0.0664	0.1231	0.1623	0.056*
H12B	−0.1315	0.3057	0.1493	0.056*
H12C	−0.0860	0.2292	0.2572	0.056*
C13	0.5222 (11)	0.6924 (9)	0.1249 (5)	0.061 (2)
H13A	0.6470	0.7301	0.1684	0.091*
H13B	0.4669	0.7775	0.0797	0.091*
H13C	0.5597	0.6014	0.0868	0.091*
C14	0.2968 (11)	0.7879 (7)	0.2460 (5)	0.0483 (17)
H14A	0.2497	0.8743	0.2002	0.072*
H14B	0.4204	0.8221	0.2917	0.072*
H14C	0.1839	0.7596	0.2834	0.072*
C15	0.2174 (8)	0.5569 (7)	0.5301 (4)	0.0301 (12)
C16	0.0480 (9)	0.4660 (7)	0.5691 (4)	0.0372 (14)
H16A	−0.0855	0.4816	0.5254	0.056*
H16B	0.0349	0.5037	0.6355	0.056*
H16C	0.0836	0.3531	0.5718	0.056*
O1	0.5017 (6)	0.5651 (5)	0.4367 (3)	0.0370 (10)
O2	0.7419 (6)	0.6310 (6)	0.3489 (3)	0.0476 (11)
O3	0.2640 (7)	0.6912 (5)	0.5555 (3)	0.0415 (10)

	U11	U22	U33	U12	U13	U23
C1	0.021 (3)	0.023 (3)	0.027 (3)	0.002 (2)	0.003 (2)	−0.003 (2)
C2	0.034 (3)	0.023 (3)	0.033 (3)	0.003 (2)	0.006 (3)	−0.001 (3)
C3	0.029 (3)	0.025 (3)	0.029 (3)	0.002 (2)	0.005 (2)	−0.005 (2)
C4	0.044 (3)	0.037 (4)	0.027 (3)	0.000 (3)	0.007 (3)	−0.005 (3)
C5	0.069 (5)	0.048 (4)	0.028 (3)	0.006 (4)	0.009 (3)	0.005 (3)
C6	0.053 (4)	0.032 (3)	0.034 (3)	0.012 (3)	0.002 (3)	0.011 (3)
C7	0.043 (3)	0.027 (3)	0.047 (3)	0.004 (3)	0.019 (3)	0.006 (3)
C8	0.026 (3)	0.024 (3)	0.037 (3)	0.000 (2)	0.014 (3)	−0.003 (2)
C9	0.018 (2)	0.027 (3)	0.052 (3)	0.004 (2)	0.010 (3)	−0.002 (3)
C10	0.026 (3)	0.023 (3)	0.030 (3)	0.001 (2)	0.003 (2)	−0.003 (2)
C11	0.022 (2)	0.027 (3)	0.022 (2)	−0.002 (2)	0.007 (2)	−0.002 (2)
C12	0.031 (3)	0.039 (4)	0.040 (3)	0.001 (3)	0.002 (3)	−0.009 (3)
C13	0.067 (5)	0.056 (5)	0.067 (4)	−0.008 (4)	0.032 (4)	0.019 (4)
C14	0.059 (4)	0.021 (3)	0.064 (4)	0.006 (3)	0.008 (4)	0.004 (3)
C15	0.031 (3)	0.030 (3)	0.027 (3)	0.013 (3)	−0.003 (2)	−0.001 (3)
C16	0.041 (3)	0.036 (3)	0.038 (3)	0.001 (3)	0.018 (3)	−0.006 (3)
O1	0.0256 (19)	0.043 (2)	0.041 (2)	−0.004 (2)	0.0022 (18)	−0.013 (2)
O2	0.023 (2)	0.044 (3)	0.077 (3)	−0.008 (2)	0.010 (2)	−0.011 (2)
O3	0.050 (3)	0.030 (2)	0.043 (2)	0.001 (2)	0.003 (2)	−0.012 (2)

C1—C2	1.503 (7)	C9—O2	1.205 (6)
C1—C8	1.507 (7)	C9—O1	1.343 (6)
C1—C11	1.520 (7)	C10—O1	1.438 (6)
C1—C3	1.523 (7)	C10—C11	1.519 (7)
C2—C3	1.505 (7)	C10—C15	1.527 (7)
C2—H2A	0.9900	C10—H10	1.0000
C2—H2B	0.9900	C11—H11A	0.9900
C3—C12	1.511 (7)	C11—H11B	0.9900
C3—C4	1.511 (7)	C12—H12A	0.9800
C4—C5	1.537 (9)	C12—H12B	0.9800
C4—H4A	0.9900	C12—H12C	0.9800
C4—H4B	0.9900	C13—H13A	0.9800
C5—C6	1.541 (8)	C13—H13B	0.9800
C5—H5A	0.9900	C13—H13C	0.9800
C5—H5B	0.9900	C14—H14A	0.9800
C6—C7	1.523 (8)	C14—H14B	0.9800
C6—H6A	0.9900	C14—H14C	0.9800
C6—H6B	0.9900	C15—O3	1.211 (7)
C7—C13	1.537 (8)	C15—C16	1.498 (8)
C7—C14	1.542 (8)	C16—H16A	0.9800
C7—C8	1.590 (7)	C16—H16B	0.9800
C8—C9	1.503 (7)	C16—H16C	0.9800
C8—H8	1.0000
C2—C1—C8	120.0 (5)	C1—C8—H8	105.9
C2—C1—C11	117.1 (5)	C7—C8—H8	105.9
C8—C1—C11	111.7 (4)	O2—C9—O1	116.9 (5)
C2—C1—C3	59.6 (3)	O2—C9—C8	122.5 (5)
C8—C1—C3	118.9 (5)	O1—C9—C8	120.6 (4)
C11—C1—C3	120.5 (4)	O1—C10—C11	114.2 (4)
C1—C2—C3	60.8 (4)	O1—C10—C15	107.3 (4)
C1—C2—H2A	117.7	C11—C10—C15	109.9 (4)
C3—C2—H2A	117.7	O1—C10—H10	108.4
C1—C2—H2B	117.7	C11—C10—H10	108.4
C3—C2—H2B	117.7	C15—C10—H10	108.4
H2A—C2—H2B	114.8	C10—C11—C1	108.3 (4)
C2—C3—C12	120.0 (5)	C10—C11—H11A	110.0
C2—C3—C4	117.3 (5)	C1—C11—H11A	110.0
C12—C3—C4	113.2 (5)	C10—C11—H11B	110.0
C2—C3—C1	59.5 (3)	C1—C11—H11B	110.0
C12—C3—C1	121.3 (4)	H11A—C11—H11B	108.4
C4—C3—C1	115.6 (5)	C3—C12—H12A	109.5
C3—C4—C5	112.1 (5)	C3—C12—H12B	109.5
C3—C4—H4A	109.2	H12A—C12—H12B	109.5
C5—C4—H4A	109.2	C3—C12—H12C	109.5
C3—C4—H4B	109.2	H12A—C12—H12C	109.5
C5—C4—H4B	109.2	H12B—C12—H12C	109.5
H4A—C4—H4B	107.9	C7—C13—H13A	109.5
C4—C5—C6	114.2 (4)	C7—C13—H13B	109.5
C4—C5—H5A	108.7	H13A—C13—H13B	109.5
C6—C5—H5A	108.7	C7—C13—H13C	109.5
C4—C5—H5B	108.7	H13A—C13—H13C	109.5
C6—C5—H5B	108.7	H13B—C13—H13C	109.5
H5A—C5—H5B	107.6	C7—C14—H14A	109.5
C7—C6—C5	118.7 (5)	C7—C14—H14B	109.5
C7—C6—H6A	107.6	H14A—C14—H14B	109.5
C5—C6—H6A	107.6	C7—C14—H14C	109.5
C7—C6—H6B	107.6	H14A—C14—H14C	109.5
C5—C6—H6B	107.6	H14B—C14—H14C	109.5
H6A—C6—H6B	107.1	O3—C15—C16	122.7 (5)
C6—C7—C13	110.3 (5)	O3—C15—C10	121.8 (5)
C6—C7—C14	106.7 (5)	C16—C15—C10	115.4 (5)
C13—C7—C14	108.4 (5)	C15—C16—H16A	109.5
C6—C7—C8	111.1 (5)	C15—C16—H16B	109.5
C13—C7—C8	108.5 (5)	H16A—C16—H16B	109.5
C14—C7—C8	111.6 (5)	C15—C16—H16C	109.5
C9—C8—C1	112.6 (4)	H16A—C16—H16C	109.5
C9—C8—C7	109.7 (5)	H16B—C16—H16C	109.5
C1—C8—C7	116.0 (4)	C9—O1—C10	123.2 (4)
C9—C8—H8	105.9

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O2i	0.99	2.40	3.184 (6)	136
C16—H16C···O2ii	0.98	2.37	3.262 (8)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯O2i	0.99	2.40	3.184 (6)	136
C16—H16C⋯O2ii	0.98	2.37	3.262 (8)	152

Symmetry codes: (i) ; (ii) .