Crystal structure of 7,7-dimethyl-6-methyl­idenetri­cyclo­[6.2.1.01,5]undecane-2-carb­oxy­lic acid

Beghidja, N.; Benayache, S.; Benayache, F.; Knight, D.W.; Kariuki, B.M.

doi:10.1107/S2056989014028254

organic compounds

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

Noureddine Beghidja,^a ‡ Samir Benayache,^a Fadila Benayache,^a David W. Knight ^b and Benson M. Kariuki ^b ^*

^aUnité de recherche VARENBIOMOL, Constantine 1 University, Constantine 25000, Algeria, and ^bSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
^*Correspondence e-mail: kariukib@cf.ac.uk

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 16 December 2014; accepted 30 December 2014; online 10 January 2015)

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.

Keywords: crystal structure; inula graveolens; hydrogen bonding.

CCDC reference: 1041493

1. 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 ).

2. Experimental

2.1. Crystal data

C₁₅H₂₂O₂
M_r = 234.33
Orthorhombic, C 222₁
a = 7.6400 (3) Å
b = 16.1700 (5) Å
c = 21.3406 (9) Å
V = 2636.39 (17) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 150 K
0.30 × 0.18 × 0.04 mm

2.2. 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

2.3. Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 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

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x+1, y, -z+{\script{1\over 2}}]$ .

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 ).

Supporting information

CCDC reference: 1041493

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2056989014028254/xu5833sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989014028254/xu5833Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989014028254/xu5833Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); 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 (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001).

Figures top

	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.

7,7-Dimethyl-6-methylidenetricyclo[6.2.1.0^1,5]undecane-2-carboxylic acid top

Crystal data top

C₁₅H₂₂O₂	D_x = 1.181 Mg m⁻³
M_r = 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 top

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

Refinement top

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(F_o²) + (0.0392P)² + 0.6557P] where P = (F_o² + 2F_c²)/3
2978 reflections	(Δ/σ)_max = 0.001
157 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₅H₂₂O₂	V = 2636.39 (17) Å³
M_r = 234.33	Z = 8
Orthorhombic, C222₁	Mo Kα radiation
a = 7.6400 (3) Å	µ = 0.08 mm⁻¹
b = 16.1700 (5) Å	T = 150 K
c = 21.3406 (9) Å	0.30 × 0.18 × 0.04 mm

Data collection top

Nonius KappaCCD diffractometer	2978 independent reflections
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	2327 reflections with I > 2σ(I)
T_min = 0.978, T_max = 0.997	R_int = 0.052
8814 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.07	Δρ_max = 0.15 e Å⁻³
2978 reflections	Δρ_min = −0.15 e Å⁻³
157 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.84	1.81	2.646 (3)	174.0

Symmetry code: (i) −x+1, y, −z+1/2.

Footnotes

‡Additional correspondence author, e-mail: nourbeghidja@yahoo.fr.

Acknowledgements

The authors extend their appreciation to Constantine 1 University and Cardiff University for supporting this research.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1992). SIR92. University of Bari, Italy. Google Scholar
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Chiappini, I. & Fardella, G. (1980). Fitoterapia, 51, 161-162. CAS Google Scholar
Dastlik, K. A., Ghisalberti, E. L., Skelton, B. W. & White, A. H. (1992). Aust. J. Chem. 45, 959–964. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Harlow, R. L. & Simonsen, S. H. (1977). Cryst. Struct. Commun. 6, 689-693. Google Scholar
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of 7,7-di­methyl-6-methyl­idenetri­cyclo­[6.2.1.01,5]undecane-2-carb­­oxy­lic acid

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Footnotes

Acknowledgements

References

organic compounds

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