Crystal structure of 7,7-dimethyl-6-methyl­idenetri­cyclo­[6.2.1.0^1,5]undecane-2-carb­oxy­lic acid

Abstract

In the title compound, C₁₅H₂₂O₂, both five-membered rings display an envelope conformation whereas the six-membered ring displays a chair conformation. In the crystal, pairs of O—H⋯O hydrogen bonds between carb­oxy­lic groups link mol­ecules, related by a twofold rotation axis, into supra­molecular dimers.

Related literature  

For background to the title compound, which was extracted from the air-dried aerial parts of inula graveolens see: Chiappini & Fardella (1980 ▸); Rustaiyan et al. (1987 ▸). For related structures, see: Turner et al. (1980 ▸); Harlow & Simonsen (1977 ▸); Dastlik et al. (1992 ▸).

Experimental  

Crystal data  

• C₁₅H₂₂O₂

• M _r = 234.33

• Orthorhombic,

• a = 7.6400 (3) Å

• b = 16.1700 (5) Å

• c = 21.3406 (9) Å

• V = 2636.39 (17) ų

• Z = 8

• Mo Kα radiation

• μ = 0.08 mm⁻¹

• T = 150 K

• 0.30 × 0.18 × 0.04 mm

Data collection  

• Nonius KappaCCD diffractometer

• Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▸) T _min = 0.978, T _max = 0.997

• 8814 measured reflections

• 2978 independent reflections

• 2327 reflections with I > 2σ(I)

• R _int = 0.052

Refinement  

• R[F ² > 2σ(F ²)] = 0.047

• wR(F ²) = 0.103

• S = 1.07

• 2978 reflections

• 157 parameters

• H-atom parameters constrained

• Δρ_max = 0.15 e Å⁻³

• Δρ_min = −0.15 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▸); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997 ▸); data reduction: HKL DENZO (Otwinowski & Minor 1997 ▸) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1992 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP99 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012 ▸) and CHEMDRAW Ultra (Cambridge Soft, 2001 ▸).

Supplementary Material

CCDC reference: 1041493

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O1H1O2i	0.84	1.81	2.646(3)	174

Symmetry code: (i) .

supplementary crystallographic information

S1. Comment

Inula graveolens have consistently been the subject of research interest (Chiappini & Fardella, 1980; Rustaiyan et al., 1987). Our interest is the extracts from aerial parts of Algerian species such as stems, flowers and leaves. The asymmetric unit of the crystal structure consists of a single molecule (Fig. 1). Both five-membered rings display an envelope conformation (with C4 and C8 as the flap atoms) whereas the six-membered ring displays a chair conformation.

The structure consists of pairs of molecules linked by the classic dimeric carbocylic acid hydrogen bonding interaction (Fig 2). Structures of some related compounds have been reported (Turner et al., 1980; Harlow & Simonsen, 1977; Dastlik et al., 1992).

S2. Experimental

The air-dried aerial parts of inula graveolens (500 g) were extracted with acetone/Et₂O (1:1) at room temperature. The solution was filtered off and concentrated under reduced pressure to give a pale yellow gum (9 g). The gum was subjected to successive column chromatography (silica gel) and TLC (silica gel, PF254). Eleven fractions were obtained. Fraction 9 gave a material which crystallized as colourless crystals with a melting point of 450 K.

S3. Refinement

H atoms were positioned geometrically and refined using a riding model with U_iso(H) constrained to be 1.2 times U_eq for the atom it is bonded to (except for methyl groups where it was 1.5 times with free rotation about the C—C bond).

Figures

Fig. 1.

A molecule showing atom labels and 50% probability displacement ellipsoids for non-H atoms.

Fig. 2.

Crystal packing in the structure with H atoms omitted and hydrogen bonds shown as dotted lines.

Crystal data

C15H22O2	Dx = 1.181 Mg m−3
Mr = 234.33	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, C2221	Cell parameters from 2327 reflections
a = 7.6400 (3) Å	θ = 2.7–27.4°
b = 16.1700 (5) Å	µ = 0.08 mm−1
c = 21.3406 (9) Å	T = 150 K
V = 2636.39 (17) Å3	Plate, colourless
Z = 8	0.30 × 0.18 × 0.04 mm
F(000) = 1024

Data collection

Nonius KappaCCD diffractometer	2978 independent reflections
Radiation source: fine-focus sealed tube	2327 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
CCD slices, ω and phi scans	θmax = 27.4°, θmin = 2.7°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −9→8
Tmin = 0.978, Tmax = 0.997	k = −20→20
8814 measured reflections	l = −27→27

Refinement

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0392P)2 + 0.6557P] where P = (Fo2 + 2Fc2)/3
2978 reflections	(Δ/σ)max = 0.001
157 parameters	Δρmax = 0.15 e Å−3
0 restraints	Δρmin = −0.15 e Å−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3233 (3)	0.41972 (11)	0.18712 (10)	0.0496 (5)
C2	0.1890 (3)	0.39139 (12)	0.14061 (9)	0.0469 (5)
H2	0.0705	0.4118	0.1532	0.056*
C3	0.1900 (2)	0.29473 (10)	0.13886 (8)	0.0351 (4)
C4	0.3048 (2)	0.27610 (11)	0.08041 (7)	0.0331 (4)
H4	0.4293	0.2879	0.0918	0.040*
C5	0.2468 (3)	0.34157 (11)	0.03307 (8)	0.0419 (4)
H5A	0.3350	0.3485	−0.0005	0.050*
H5B	0.1330	0.3268	0.0139	0.050*
C7	0.2312 (3)	0.41978 (13)	0.07268 (9)	0.0586 (6)
H7A	0.1365	0.4556	0.0564	0.070*
H7B	0.3423	0.4513	0.0718	0.070*
C8	0.2606 (3)	0.24567 (10)	0.19461 (7)	0.0355 (4)
H8A	0.2004	0.2609	0.2340	0.043*
H8B	0.3884	0.2534	0.1997	0.043*
C9	0.2161 (2)	0.15726 (11)	0.17434 (7)	0.0348 (4)
H9	0.2277	0.1182	0.2104	0.042*
C10	0.0230 (2)	0.16680 (12)	0.15525 (8)	0.0415 (4)
H10A	−0.0550	0.1569	0.1915	0.050*
H10B	−0.0075	0.1273	0.1215	0.050*
C11	0.0058 (3)	0.25713 (12)	0.13183 (9)	0.0422 (5)
H11A	−0.0323	0.2584	0.0875	0.051*
H11B	−0.0801	0.2880	0.1575	0.051*
C12	0.3311 (2)	0.12798 (11)	0.11790 (8)	0.0345 (4)
C13	0.2924 (2)	0.18576 (11)	0.06300 (7)	0.0330 (4)
C14	0.5274 (2)	0.13066 (12)	0.13538 (9)	0.0428 (4)
H14A	0.5965	0.1063	0.1014	0.064*
H14B	0.5465	0.0992	0.1740	0.064*
H14C	0.5634	0.1882	0.1418	0.064*
C15	0.2877 (3)	0.03737 (11)	0.10297 (9)	0.0504 (5)
H15A	0.1635	0.0326	0.0922	0.076*
H15B	0.3129	0.0030	0.1397	0.076*
H15C	0.3591	0.0187	0.0675	0.076*
C16	0.2421 (2)	0.16103 (13)	0.00671 (8)	0.0462 (5)
H16A	0.2123	0.2007	−0.0244	0.055*
H16B	0.2358	0.1037	−0.0026	0.055*
O1	0.2608 (2)	0.42962 (10)	0.24438 (7)	0.0639 (4)
H1	0.3442	0.4330	0.2699	0.096*
O2	0.4779 (2)	0.42873 (9)	0.17426 (7)	0.0606 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0665 (16)	0.0313 (9)	0.0511 (12)	0.0092 (10)	0.0070 (11)	−0.0002 (9)
C2	0.0534 (13)	0.0419 (10)	0.0455 (11)	0.0164 (9)	0.0036 (10)	0.0009 (9)
C3	0.0345 (10)	0.0406 (10)	0.0302 (8)	0.0087 (8)	0.0013 (8)	−0.0016 (7)
C4	0.0282 (9)	0.0425 (9)	0.0286 (8)	0.0027 (8)	0.0001 (7)	0.0016 (7)
C5	0.0381 (11)	0.0547 (11)	0.0329 (8)	0.0078 (9)	0.0026 (8)	0.0100 (8)
C7	0.0752 (17)	0.0499 (12)	0.0507 (11)	0.0192 (11)	0.0035 (11)	0.0137 (9)
C8	0.0405 (10)	0.0413 (10)	0.0248 (8)	0.0060 (8)	0.0006 (7)	−0.0018 (7)
C9	0.0345 (10)	0.0433 (10)	0.0265 (8)	0.0004 (8)	0.0025 (7)	0.0029 (7)
C10	0.0338 (10)	0.0583 (12)	0.0326 (9)	−0.0032 (9)	0.0092 (8)	0.0004 (8)
C11	0.0310 (10)	0.0622 (12)	0.0335 (9)	0.0088 (9)	0.0067 (8)	0.0038 (8)
C12	0.0348 (10)	0.0347 (9)	0.0341 (9)	0.0009 (8)	0.0049 (8)	−0.0032 (7)
C13	0.0237 (9)	0.0458 (10)	0.0296 (8)	−0.0001 (7)	0.0063 (7)	−0.0030 (7)
C14	0.0360 (11)	0.0432 (10)	0.0492 (11)	0.0064 (8)	−0.0006 (8)	0.0046 (9)
C15	0.0534 (14)	0.0422 (11)	0.0558 (12)	−0.0047 (9)	0.0107 (11)	−0.0075 (9)
C16	0.0405 (12)	0.0621 (12)	0.0361 (9)	−0.0022 (10)	0.0062 (9)	−0.0090 (9)
O1	0.0667 (11)	0.0715 (9)	0.0536 (8)	0.0157 (8)	0.0057 (8)	−0.0223 (8)
O2	0.0667 (11)	0.0592 (9)	0.0560 (9)	−0.0160 (8)	0.0063 (8)	0.0078 (7)

Geometric parameters (Å, º)

C1—O2	1.221 (3)	C9—C12	1.564 (2)
C1—O1	1.322 (2)	C9—H9	1.0000
C1—C2	1.499 (3)	C10—C11	1.549 (3)
C2—C7	1.555 (3)	C10—H10A	0.9900
C2—C3	1.564 (2)	C10—H10B	0.9900
C2—H2	1.0000	C11—H11A	0.9900
C3—C8	1.529 (2)	C11—H11B	0.9900
C3—C11	1.540 (3)	C12—C13	1.527 (2)
C3—C4	1.554 (2)	C12—C15	1.536 (2)
C4—C13	1.510 (2)	C12—C14	1.546 (3)
C4—C5	1.529 (2)	C13—C16	1.323 (2)
C4—H4	1.0000	C14—H14A	0.9800
C5—C7	1.526 (3)	C14—H14B	0.9800
C5—H5A	0.9900	C14—H14C	0.9800
C5—H5B	0.9900	C15—H15A	0.9800
C7—H7A	0.9900	C15—H15B	0.9800
C7—H7B	0.9900	C15—H15C	0.9800
C8—C9	1.532 (2)	C16—H16A	0.9500
C8—H8A	0.9900	C16—H16B	0.9500
C8—H8B	0.9900	O1—H1	0.8400
C9—C10	1.538 (3)
O2—C1—O1	122.9 (2)	C10—C9—C12	111.40 (14)
O2—C1—C2	123.34 (19)	C8—C9—H9	110.6
O1—C1—C2	113.7 (2)	C10—C9—H9	110.6
C1—C2—C7	112.66 (19)	C12—C9—H9	110.6
C1—C2—C3	108.54 (15)	C9—C10—C11	105.13 (15)
C7—C2—C3	105.77 (15)	C9—C10—H10A	110.7
C1—C2—H2	109.9	C11—C10—H10A	110.7
C7—C2—H2	109.9	C9—C10—H10B	110.7
C3—C2—H2	109.9	C11—C10—H10B	110.7
C8—C3—C11	101.16 (14)	H10A—C10—H10B	108.8
C8—C3—C4	108.95 (13)	C3—C11—C10	105.28 (14)
C11—C3—C4	111.16 (14)	C3—C11—H11A	110.7
C8—C3—C2	120.12 (14)	C10—C11—H11A	110.7
C11—C3—C2	113.12 (15)	C3—C11—H11B	110.7
C4—C3—C2	102.45 (14)	C10—C11—H11B	110.7
C13—C4—C5	119.27 (15)	H11A—C11—H11B	108.8
C13—C4—C3	110.45 (14)	C13—C12—C15	112.50 (15)
C5—C4—C3	103.45 (13)	C13—C12—C14	110.84 (14)
C13—C4—H4	107.7	C15—C12—C14	106.63 (15)
C5—C4—H4	107.7	C13—C12—C9	107.26 (13)
C3—C4—H4	107.7	C15—C12—C9	109.12 (15)
C7—C5—C4	103.33 (14)	C14—C12—C9	110.51 (14)
C7—C5—H5A	111.1	C16—C13—C4	122.27 (17)
C4—C5—H5A	111.1	C16—C13—C12	124.60 (17)
C7—C5—H5B	111.1	C4—C13—C12	113.00 (14)
C4—C5—H5B	111.1	C12—C14—H14A	109.5
H5A—C5—H5B	109.1	C12—C14—H14B	109.5
C5—C7—C2	106.75 (16)	H14A—C14—H14B	109.5
C5—C7—H7A	110.4	C12—C14—H14C	109.5
C2—C7—H7A	110.4	H14A—C14—H14C	109.5
C5—C7—H7B	110.4	H14B—C14—H14C	109.5
C2—C7—H7B	110.4	C12—C15—H15A	109.5
H7A—C7—H7B	108.6	C12—C15—H15B	109.5
C3—C8—C9	100.72 (13)	H15A—C15—H15B	109.5
C3—C8—H8A	111.6	C12—C15—H15C	109.5
C9—C8—H8A	111.6	H15A—C15—H15C	109.5
C3—C8—H8B	111.6	H15B—C15—H15C	109.5
C9—C8—H8B	111.6	C13—C16—H16A	120.0
H8A—C8—H8B	109.4	C13—C16—H16B	120.0
C8—C9—C10	101.20 (14)	H16A—C16—H16B	120.0
C8—C9—C12	112.04 (14)	C1—O1—H1	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2i	0.84	1.81	2.646 (3)	174

Symmetry code: (i) −x+1, y, −z+1/2.