1,4a-Dimethyl-6-methyl­ene-5-(5,5,6,6-tetra­cyano-2-methyl­cyclo­hex-2-enylmeth­yl)deca­hydro­naphthalene-1-carboxylic acid: a trans-communic acid derivative

Rejouani, N.; Auhmani, A.; Ait Itto, M.Y.; Benharref, A.; Daran, J.-C.

doi:10.1107/S1600536808001086

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o475

doi:10.1107/S1600536808001086

Open

access

1,4a-Dimethyl-6-methylene-5-(5,5,6,6-tetracyano-2-methylcyclohex-2-enylmethyl)decahydronaphthalene-1-carboxylic acid: a trans-communic acid derivative

Nezha Rejouani,^a Aziz Auhmani,^a My Youssef Ait Itto,^a Ahmed Benharref ^a and Jean-Claude Daran ^b ^*

^aLaboratoire de Chimie Biomoléculaire, Substances Naturelles et Réactivité, Equipe de Chimie des Substances Naturelles, Département de Chimie, Faculté des Sciences Semlalia, BP 2390 Marrakech, Morocco, and ^bLaboratoire de Chimie de Coordination, UPR CNRS 8241, 205 route de Narbonne, 31077 Toulouse Cedex, France
^*Correspondence e-mail: daran@lcc-toulouse.fr

(Received 18 September 2007; accepted 10 January 2008; online 18 January 2008)

In the search for cancer chemopreventive agents, we have studied the Diels–Alder reaction of trans-communic acid with tetracyanoethylene in the presence of SiO₂ as catalyst. The title cycloadduct, C₂₆H₃₀N₄O₂, was obtained in 75% yield. The molecules are arranged in pairs through O—H⋯O hydrogen bonds, forming an R₂²(8) ring motif. Both the fused cyclohexyl rings adopt a chair conformation, whereas the nonfused ring adopts a half-chair conformation.

Related literature

For literature on anti-tumour activity, see: Bouhal et al. (1988 ); Iwamoto et al. (2001 ). For structural analyses, see: Etter et al. (1990 ); Bernstein et al. (1995 ); Cremer & Pople (1975 ). For the treatment of disordered solvent, see: Spek (2003 ).

Experimental

Crystal data

C₂₆H₃₀N₄O₂
M_r = 430.54
Monoclinic, C 2
a = 30.664 (4) Å
b = 11.8233 (19) Å
c = 7.1857 (10) Å
β = 93.260 (12)°
V = 2600.9 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 180 (2) K
0.52 × 0.08 × 0.07 mm

Data collection

Oxford Diffraction Xcalibur Sapphire-I diffractometer
Absorption correction: none
5114 measured reflections
2615 independent reflections
1302 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.085
S = 0.82
2615 reflections
293 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9⋯O9′ⁱ	0.84	1.79	2.631 (3)	178
Symmetry code: (i) -x+1, y, -z+1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Versions 1.171.31.5. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Versions 1.171.31.5. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808001086/er2042sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808001086/er2042Isup2.hkl

checkCIF report

Comment top

Juniperus oxycedrus has been used in traditional folk medicine for the treatment of chronic eczema and other several skin diseases (Bouhal et al., 1988). Trans communic acid 1 is one of the compounds which were isolated from Juniperusoxycedrus and known by its moderate anti-tumor activity (Iwamoto et al., 2001). In the search for cancer chemo preventive agents with strong activity, we have studied the Diels-Alder reaction of trans communic acid 1 with tetracyanoethylene 2 in the presence of SiO₂ as catalyst (Fig.1). One cycloadduct 3 was obtained in 75% yield.

Its structure was identified as 1,4a-Dimethyl-6-methylene-5-(5,5,6,6-tetracyano-2-methylcyclohex-2-εnylmethyl)-decahydronaphthalene-1-carboxylic acid using spectral methods including ¹H and ¹³C NMR and confirmed by an X-ray crystallographic analysis. The ¹H NMR spectrum of 3 exhibits three methyl singlets at 1.96, 1.29 and 0.69 p.p.m., a triplet (J=3 Hz, at 5.57ppm) due to proton H-3' and two singlets (at 4.50 and 5.08 p.p.m.) assigned to methylenic protons at 13 position. The ¹³C NMR spectra reveals twenty six signals including specially a carbonyl group at 183.36 p.p.m. and four cyano group signals at 109.19; 110.07; 110.94 and 111.54ppm.

The molecule is build up by two fused six cyclohexyl rings linked linked through a CH₂ spacer to a tetracyano-2-methylcyclohexyl ring (Fig. 2). The fused cyclohexyl rings, C1 to C8a and C4A to C8A, adopt a chair conformation as indicated by the puckering parameters [Q= 0.533 (6)°, 0.576 (6)° and θ= 0. 0(6)°, 0.4 (6)°, Cremer & Pople, (1975)]. The non fused cyclohexyl ring adopt a half-chair conformation[Q= 0.510 (6)° and θ= 50.7 (5)°]. The occurrence of O—H···O hydrogen bonds form pairs of molecules through a R²₂(8) ring motif (Etter et al., 1990; Bernstein et al., 1995) (Fig. 3).

Related literature top

For literature on anti-tumour activity, see: Bouhal et al. (1988); Iwamoto et al. (2001). For structural analyses, see: Etter et al. (1990); Bernstein et al. (1995); Cremer & Pople (1975). For related literature, see: Spek (2003).

Experimental top

To a solution of Compound 1(1 g, 2.5 mmol) in 20 ml of dichloromethane, was added tetracyanoethylene (TCNE)(0.32 g, 2.5 mmol). The mixture was refluxed for 72 h. After cooling, the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by chromatography on silica gel column (eluent: hexane/ethyl acetate 90/10), then the isolated product was recrystallized from ethyl acetate to give compound 3(750 mg, 75%).

Colourless crystal, mp=208–210°C (ethyl acetate). ¹H NMR (300 MHz, CDCl₃)δ (p.p.m.): 5.57 (t, 1H, J=4.45 Hz); 5.08 (s, 1H); 4.50 (s,1H); 3.28 (br d,1H, J=11.5 Hz); 3.00 (m, 2H); 2.48 (br d, 1H, J=11.5 Hz); 2.29–1.96 (m, 5H); 1.92 (s, 3H); 1.81 (m, 3H); 1.62 (m, 1H); 1.45 (dd, 1H, J=12.21 and 2.60); 1.29 (s, 3H); 1.26 (m, 2H); 1.15 (m, 1H); 0.69 (s, 3H). ¹³C NMR δ (p.p.m.) CDCl₃: 12.64 C11, 19.85 C3, 21.78 C7, 25.59 C8, 26.13 C4, 29.01 C9, 31.75 C12, 37.70 C2, 38.07 C4', 38.58 C7, 39.56 C4a, 41.37 C6', 41.74 C1', 43.41 C5', 44.29 C1, 51.63 C5, 56.47 C8a, 107.59 C13, 109.19 C8', 110.07 C9', 110.94 C10', 111.54 C11', 116.37 C3', 135.27 C6, 147.14 C2', 183.36 C10

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Scheme showing the synthetic pathway for the title compound.
	Fig. 2. Molecular view of compound 3 with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 3. Partial packing view showing pair of molecules connected by O—H···O hydrogen bonds and forming a R₂²(8) ring motif. Hydrogen bonds are shown as dashed lines. Hydrogen not involved in hydrogen bonding have been omitted for clarity. [Symmetry code: (i) 1 - x, y, 1 - z].

1,4a-Dimethyl-6-methylene-5-(5,5,6,6-tetracyano-2-methylcyclohex-2- enylmethyl)decahydronaphthalene-1-carboxylic acid ? top

Crystal data top

C₂₆H₃₀N₄O₂	F(000) = 920
M_r = 430.54	D_x = 1.099 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 907 reflections
a = 30.664 (4) Å	θ = 3.1–26.4°
b = 11.8233 (19) Å	µ = 0.07 mm⁻¹
c = 7.1857 (10) Å	T = 180 K
β = 93.260 (12)°	Needle, colorless
V = 2600.9 (6) Å³	0.52 × 0.08 × 0.07 mm
Z = 4

Data collection top

Oxford-Diffraction Xcalibur Sapphire-I diffractometer	1302 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.037
Graphite monochromator	θ_max = 26.4°, θ_min = 3.1°
Detector resolution: 8.2632 pixels mm^-1	h = −23→38
ω and ϕ scans	k = −11→14
5114 measured reflections	l = −7→8
2615 independent reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 0.82	w = 1/[σ²(F_o²) + (0.0416P)²] where P = (F_o² + 2F_c²)/3
2615 reflections	(Δ/σ)_max = 0.003
293 parameters	Δρ_max = 0.13 e Å⁻³
1 restraint	Δρ_min = −0.12 e Å⁻³

Crystal data top

C₂₆H₃₀N₄O₂	V = 2600.9 (6) Å³
M_r = 430.54	Z = 4
Monoclinic, C2	Mo Kα radiation
a = 30.664 (4) Å	µ = 0.07 mm⁻¹
b = 11.8233 (19) Å	T = 180 K
c = 7.1857 (10) Å	0.52 × 0.08 × 0.07 mm
β = 93.260 (12)°

Data collection top

Oxford-Diffraction Xcalibur Sapphire-I diffractometer	1302 reflections with I > 2σ(I)
5114 measured reflections	R_int = 0.037
2615 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.085	H-atom parameters constrained
S = 0.82	Δρ_max = 0.13 e Å⁻³
2615 reflections	Δρ_min = −0.12 e Å⁻³
293 parameters

Special details top

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.

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 > σ(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	0.59538 (10)	0.4362 (3)	0.2817 (5)	0.0536 (10)
C1'	0.64958 (9)	−0.0975 (3)	0.2534 (4)	0.0364 (9)
H1'	0.6284	−0.1263	0.1537	0.044*
C2'	0.65560 (10)	−0.1895 (3)	0.3989 (4)	0.0398 (9)
C2	0.63385 (10)	0.4539 (3)	0.4201 (6)	0.0623 (11)
H2A	0.6608	0.4605	0.3509	0.075*
H2B	0.6298	0.5262	0.4864	0.075*
C3'	0.69097 (10)	−0.2504 (3)	0.4250 (4)	0.0507 (10)
H3'	0.6914	−0.3052	0.5217	0.061*
C3	0.63991 (10)	0.3605 (3)	0.5617 (5)	0.0592 (11)
H3A	0.6147	0.3597	0.6416	0.071*
H3B	0.6665	0.3757	0.6424	0.071*
C4	0.64403 (10)	0.2457 (3)	0.4706 (5)	0.0495 (10)
H4A	0.6458	0.1869	0.5689	0.059*
H4B	0.6716	0.2433	0.4055	0.059*
C4'	0.73066 (10)	−0.2407 (3)	0.3154 (5)	0.0529 (10)
H4'A	0.7427	−0.3170	0.2938	0.063*
H4'B	0.7532	−0.1960	0.3865	0.063*
C4A	0.60575 (9)	0.2174 (3)	0.3301 (4)	0.0361 (9)
C5	0.61843 (9)	0.1098 (3)	0.2159 (4)	0.0351 (8)
H5	0.6457	0.1294	0.1529	0.042*
C5'	0.71920 (10)	−0.1833 (3)	0.1284 (5)	0.0481 (10)
C6	0.58379 (11)	0.0870 (4)	0.0639 (5)	0.0494 (10)
C6'	0.69273 (9)	−0.0707 (3)	0.1609 (5)	0.0417 (9)
C7'	0.61661 (10)	−0.2127 (3)	0.5115 (5)	0.0564 (11)
H7'A	0.6219	−0.2811	0.5866	0.085*
H7'B	0.5907	−0.2239	0.4272	0.085*
H7'C	0.6118	−0.1484	0.5939	0.085*
C7	0.57720 (12)	0.1836 (4)	−0.0693 (5)	0.0692 (13)
H7A	0.5535	0.1652	−0.1636	0.083*
H7B	0.6043	0.1966	−0.1350	0.083*
C8'	0.69222 (12)	−0.2582 (4)	0.0066 (6)	0.0508 (10)
C8	0.56546 (11)	0.2901 (3)	0.0358 (5)	0.0593 (12)
H8A	0.5366	0.2797	0.0887	0.071*
H8B	0.5631	0.3545	−0.0523	0.071*
C8A	0.59952 (10)	0.3178 (3)	0.1931 (5)	0.0472 (10)
H8	0.6277	0.3213	0.1297	0.057*
C9	0.55363 (10)	0.4563 (3)	0.3803 (6)	0.0470 (10)
C9'	0.75865 (11)	−0.1575 (4)	0.0316 (5)	0.0602 (11)
C10'	0.72097 (11)	0.0021 (3)	0.2844 (6)	0.0548 (11)
C10	0.59748 (14)	0.5294 (3)	0.1310 (6)	0.0858 (16)
H10A	0.5710	0.5266	0.0482	0.129*
H10B	0.6231	0.5170	0.0581	0.129*
H10C	0.5997	0.6037	0.1913	0.129*
C11	0.56460 (9)	0.1932 (3)	0.4331 (4)	0.0438 (9)
H11A	0.5700	0.1298	0.5190	0.066*
H11B	0.5406	0.1739	0.3428	0.066*
H11C	0.5567	0.2605	0.5035	0.066*
C11'	0.68511 (11)	−0.0140 (3)	−0.0200 (6)	0.0486 (10)
C12	0.62924 (10)	0.0071 (3)	0.3388 (4)	0.0403 (9)
H12A	0.6019	−0.0172	0.3937	0.048*
H12B	0.6493	0.0326	0.4431	0.048*
C13	0.55899 (11)	−0.0039 (4)	0.0508 (5)	0.0696 (13)
H13A	0.5364	−0.0090	−0.0448	0.084*
H13B	0.5637	−0.0642	0.1368	0.084*
N8'	0.67137 (11)	−0.3154 (3)	−0.0892 (5)	0.0749 (11)
N9'	0.78989 (10)	−0.1379 (4)	−0.0408 (5)	0.0974 (14)
N10'	0.74280 (11)	0.0563 (3)	0.3805 (5)	0.0864 (13)
N11'	0.68067 (11)	0.0254 (3)	−0.1637 (5)	0.0767 (11)
O9	0.51784 (7)	0.4467 (2)	0.2691 (3)	0.0616 (8)
H9	0.4958	0.4589	0.3303	0.092*
O9'	0.55236 (7)	0.4807 (2)	0.5443 (4)	0.0569 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.042 (2)	0.056 (3)	0.065 (3)	0.0049 (18)	0.023 (2)	0.014 (2)
C1'	0.0289 (17)	0.047 (2)	0.034 (2)	−0.0031 (15)	0.0035 (16)	−0.0048 (18)
C2'	0.043 (2)	0.044 (2)	0.032 (2)	−0.0001 (17)	0.0037 (15)	−0.0009 (19)
C2	0.0362 (19)	0.046 (3)	0.106 (3)	−0.0033 (18)	0.020 (2)	−0.002 (3)
C3'	0.057 (2)	0.060 (3)	0.035 (2)	0.008 (2)	0.0042 (18)	0.008 (2)
C3	0.041 (2)	0.056 (3)	0.079 (3)	−0.0013 (19)	−0.0142 (19)	−0.016 (3)
C4	0.0387 (19)	0.058 (3)	0.051 (2)	0.0003 (18)	−0.0047 (16)	−0.001 (2)
C4'	0.047 (2)	0.071 (3)	0.041 (2)	0.0157 (19)	−0.0008 (17)	0.009 (2)
C4A	0.0301 (17)	0.046 (2)	0.033 (2)	0.0065 (15)	0.0034 (15)	0.0118 (18)
C5	0.0336 (18)	0.045 (2)	0.027 (2)	0.0009 (15)	0.0025 (15)	0.0057 (19)
C5'	0.0338 (19)	0.065 (3)	0.046 (2)	0.0010 (19)	0.0073 (17)	0.000 (2)
C6	0.042 (2)	0.071 (3)	0.035 (2)	0.011 (2)	0.0020 (18)	−0.005 (2)
C6'	0.0365 (18)	0.049 (2)	0.040 (2)	−0.0049 (17)	0.0040 (16)	0.002 (2)
C7'	0.053 (2)	0.071 (3)	0.046 (2)	0.0026 (18)	0.0139 (17)	0.016 (2)
C7	0.074 (3)	0.105 (4)	0.029 (2)	0.036 (2)	0.0067 (18)	0.007 (3)
C8'	0.053 (3)	0.057 (3)	0.043 (3)	0.005 (2)	0.013 (2)	0.009 (2)
C8	0.064 (2)	0.086 (3)	0.028 (2)	0.033 (2)	0.0061 (18)	0.014 (2)
C8A	0.0355 (18)	0.065 (3)	0.043 (2)	0.0142 (17)	0.0170 (16)	0.009 (2)
C9	0.039 (2)	0.043 (2)	0.059 (3)	0.0040 (16)	0.006 (2)	0.020 (2)
C9'	0.049 (2)	0.082 (3)	0.050 (3)	0.006 (2)	0.0087 (19)	−0.001 (2)
C10'	0.039 (2)	0.060 (3)	0.067 (3)	−0.0105 (19)	0.013 (2)	−0.007 (2)
C10	0.100 (3)	0.060 (3)	0.104 (4)	0.018 (2)	0.059 (3)	0.047 (3)
C11	0.042 (2)	0.060 (3)	0.030 (2)	−0.0030 (17)	0.0069 (16)	−0.001 (2)
C11'	0.052 (2)	0.046 (3)	0.049 (3)	0.0067 (18)	0.017 (2)	0.010 (2)
C12	0.0415 (18)	0.048 (2)	0.031 (2)	−0.0010 (16)	0.0030 (15)	0.0012 (18)
C13	0.046 (2)	0.099 (4)	0.062 (3)	0.011 (3)	−0.015 (2)	−0.004 (3)
N8'	0.089 (3)	0.084 (3)	0.053 (2)	−0.013 (2)	0.016 (2)	−0.005 (2)
N9'	0.057 (2)	0.143 (4)	0.095 (3)	0.001 (2)	0.032 (2)	0.004 (3)
N10'	0.063 (2)	0.101 (3)	0.095 (3)	−0.031 (2)	0.008 (2)	−0.042 (3)
N11'	0.094 (3)	0.088 (3)	0.051 (2)	0.023 (2)	0.028 (2)	0.019 (2)
O9	0.0462 (14)	0.092 (2)	0.0471 (15)	0.0210 (14)	0.0064 (12)	0.0007 (16)
O9'	0.0444 (13)	0.075 (2)	0.0519 (16)	−0.0021 (12)	0.0105 (13)	−0.0057 (16)

Geometric parameters (Å, º) top

C1—C2	1.513 (5)	C5'—C6'	1.584 (5)
C1—C9	1.517 (5)	C6—C13	1.316 (5)
C1—C8A	1.546 (5)	C6—C7	1.497 (5)
C1—C10	1.549 (5)	C6'—C11'	1.470 (5)
C1'—C2'	1.513 (4)	C6'—C10'	1.480 (5)
C1'—C12	1.529 (4)	C7'—H7'A	0.9800
C1'—C6'	1.547 (4)	C7'—H7'B	0.9800
C1'—H1'	1.0000	C7'—H7'C	0.9800
C2'—C3'	1.306 (4)	C7—C8	1.521 (5)
C2'—C7'	1.506 (4)	C7—H7A	0.9900
C2—C3	1.506 (5)	C7—H7B	0.9900
C2—H2A	0.9900	C8'—N8'	1.136 (5)
C2—H2B	0.9900	C8—C8A	1.530 (5)
C3'—C4'	1.491 (4)	C8—H8A	0.9900
C3'—H3'	0.9500	C8—H8B	0.9900
C3—C4	1.516 (5)	C8A—H8	1.0000
C3—H3A	0.9900	C9—O9'	1.216 (4)
C3—H3B	0.9900	C9—O9	1.325 (4)
C4—C4A	1.541 (4)	C9'—N9'	1.139 (4)
C4—H4A	0.9900	C10'—N10'	1.133 (4)
C4—H4B	0.9900	C10—H10A	0.9800
C4'—C5'	1.528 (5)	C10—H10B	0.9800
C4'—H4'A	0.9900	C10—H10C	0.9800
C4'—H4'B	0.9900	C11—H11A	0.9800
C4A—C11	1.526 (4)	C11—H11B	0.9800
C4A—C8A	1.547 (4)	C11—H11C	0.9800
C4A—C5	1.574 (4)	C11'—N11'	1.134 (4)
C5—C6	1.504 (4)	C12—H12A	0.9900
C5—C12	1.527 (4)	C12—H12B	0.9900
C5—H5	1.0000	C13—H13A	0.9500
C5'—C9'	1.462 (5)	C13—H13B	0.9500
C5'—C8'	1.466 (5)	O9—H9	0.8400

C2—C1—C9	108.6 (3)	C13—C6—C5	125.4 (4)
C2—C1—C8A	108.5 (3)	C7—C6—C5	113.1 (3)
C9—C1—C8A	115.2 (3)	C11'—C6'—C10'	108.8 (3)
C2—C1—C10	107.4 (3)	C11'—C6'—C1'	112.1 (3)
C9—C1—C10	106.5 (3)	C10'—C6'—C1'	110.3 (3)
C8A—C1—C10	110.4 (3)	C11'—C6'—C5'	108.0 (3)
C2'—C1'—C12	109.9 (2)	C10'—C6'—C5'	106.9 (3)
C2'—C1'—C6'	111.7 (2)	C1'—C6'—C5'	110.5 (3)
C12—C1'—C6'	112.7 (3)	C2'—C7'—H7'A	109.5
C2'—C1'—H1'	107.4	C2'—C7'—H7'B	109.5
C12—C1'—H1'	107.4	H7'A—C7'—H7'B	109.5
C6'—C1'—H1'	107.4	C2'—C7'—H7'C	109.5
C3'—C2'—C7'	120.0 (3)	H7'A—C7'—H7'C	109.5
C3'—C2'—C1'	124.3 (3)	H7'B—C7'—H7'C	109.5
C7'—C2'—C1'	115.7 (3)	C6—C7—C8	110.0 (3)
C3—C2—C1	113.8 (3)	C6—C7—H7A	109.7
C3—C2—H2A	108.8	C8—C7—H7A	109.7
C1—C2—H2A	108.8	C6—C7—H7B	109.7
C3—C2—H2B	108.8	C8—C7—H7B	109.7
C1—C2—H2B	108.8	H7A—C7—H7B	108.2
H2A—C2—H2B	107.7	N8'—C8'—C5'	179.3 (4)
C2'—C3'—C4'	125.3 (3)	C7—C8—C8A	111.9 (3)
C2'—C3'—H3'	117.3	C7—C8—H8A	109.2
C4'—C3'—H3'	117.3	C8A—C8—H8A	109.2
C2—C3—C4	112.0 (3)	C7—C8—H8B	109.2
C2—C3—H3A	109.2	C8A—C8—H8B	109.2
C4—C3—H3A	109.2	H8A—C8—H8B	107.9
C2—C3—H3B	109.2	C8—C8A—C4A	111.1 (3)
C4—C3—H3B	109.2	C8—C8A—C1	115.4 (3)
H3A—C3—H3B	107.9	C4A—C8A—C1	116.3 (3)
C3—C4—C4A	113.5 (3)	C8—C8A—H8	104.1
C3—C4—H4A	108.9	C4A—C8A—H8	104.1
C4A—C4—H4A	108.9	C1—C8A—H8	104.1
C3—C4—H4B	108.9	O9'—C9—O9	122.3 (3)
C4A—C4—H4B	108.9	O9'—C9—C1	124.4 (3)
H4A—C4—H4B	107.7	O9—C9—C1	113.4 (3)
C3'—C4'—C5'	110.2 (3)	N9'—C9'—C5'	178.7 (4)
C3'—C4'—H4'A	109.6	N10'—C10'—C6'	178.9 (5)
C5'—C4'—H4'A	109.6	C1—C10—H10A	109.5
C3'—C4'—H4'B	109.6	C1—C10—H10B	109.5
C5'—C4'—H4'B	109.6	H10A—C10—H10B	109.5
H4'A—C4'—H4'B	108.1	C1—C10—H10C	109.5
C11—C4A—C4	110.1 (3)	H10A—C10—H10C	109.5
C11—C4A—C8A	112.1 (2)	H10B—C10—H10C	109.5
C4—C4A—C8A	108.2 (3)	C4A—C11—H11A	109.5
C11—C4A—C5	109.7 (3)	C4A—C11—H11B	109.5
C4—C4A—C5	108.4 (2)	H11A—C11—H11B	109.5
C8A—C4A—C5	108.3 (2)	C4A—C11—H11C	109.5
C6—C5—C12	113.5 (3)	H11A—C11—H11C	109.5
C6—C5—C4A	109.8 (3)	H11B—C11—H11C	109.5
C12—C5—C4A	113.2 (2)	N11'—C11'—C6'	176.2 (4)
C6—C5—H5	106.6	C5—C12—C1'	119.4 (2)
C12—C5—H5	106.6	C5—C12—H12A	107.5
C4A—C5—H5	106.6	C1'—C12—H12A	107.5
C9'—C5'—C8'	107.2 (3)	C5—C12—H12B	107.5
C9'—C5'—C4'	110.8 (3)	C1'—C12—H12B	107.5
C8'—C5'—C4'	110.5 (3)	H12A—C12—H12B	107.0
C9'—C5'—C6'	109.9 (3)	C6—C13—H13A	120.0
C8'—C5'—C6'	108.6 (3)	C6—C13—H13B	120.0
C4'—C5'—C6'	109.7 (3)	H13A—C13—H13B	120.0
C13—C6—C7	121.4 (4)	C9—O9—H9	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···O9′ⁱ	0.84	1.79	2.631 (3)	178

Symmetry code: (i) −x+1, y, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₆H₃₀N₄O₂
M_r	430.54
Crystal system, space group	Monoclinic, C2
Temperature (K)	180
a, b, c (Å)	30.664 (4), 11.8233 (19), 7.1857 (10)
β (°)	93.260 (12)
V (Å³)	2600.9 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.52 × 0.08 × 0.07

Data collection
Diffractometer	Oxford-Diffraction Xcalibur Sapphire-I diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5114, 2615, 1302
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.085, 0.82
No. of reflections	2615
No. of parameters	293
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.12

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···O9'ⁱ	0.84	1.79	2.631 (3)	177.7

Symmetry code: (i) −x+1, y, −z+1.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bouhal, K., Meynadier, J. M., Peyron, J. L., Peyron, L., Marion, J. P., Bonetti, G. & Meynadier, J. (1988). Le Cade en Dermatologie, Parfums, Cosmétiques et Aromes, 83, 73–82. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Iwamoto, M., Ohtsu, H., Tokuda, H., Nishino, H., Matasunaga, S. & Tanaka, R. (2001). Bioorg. Med. Chem. 9, 1911–1921. Web of Science CrossRef PubMed CAS Google Scholar
Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Versions 1.171.31.5. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o475

doi:10.1107/S1600536808001086

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1,4a-Di­methyl-6-methyl­ene-5-(5,5,6,6-tetra­cyano-2-methyl­cyclo­hex-2-enylmeth­yl)deca­hydro­naphthalene-1-carboxylic acid: a trans-communic acid derivative

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

1,4a-Dimethyl-6-methylene-5-(5,5,6,6-tetracyano-2-methylcyclohex-2-enylmethyl)decahydronaphthalene-1-carboxylic acid: a trans-communic acid derivative