6-Methyl-1-(nitro­meth­yl)-4-(propan-2-yl)naphthalene

Dakir, M.; Benharref, A.; El Ammari, L.; Saadi, M.; Oukhrib, A.; Berraho, M.

doi:10.1107/S2414314618002742

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 2| February 2018| x180274

https://doi.org/10.1107/S2414314618002742

Open

access

6-Methyl-1-(nitromethyl)-4-(propan-2-yl)naphthalene

Mohamed Dakir,^a ^* Ahmed Benharref,^a Lahcen El Ammari,^b Mohamed Saadi,^b Abdelouahd Oukhrib ^a and Moha Berraho ^a

^aLaboratoire de Chimie des Substances Naturelles, `Unité Associé au CNRST (URAC16)', Faculté des Sciences Semlalia, BP 2390 Bd My Abdellah, Université Cadi Ayyad, 40000 Marrakech, Morocco, and ^bLaboratoire de Chimie du Solide, Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, BP 1014, Avenue Ibn Battouta, Rabat, Morocco
^*Correspondence e-mail: dakirmohamed18@gmail.com

Edited by K. Fejfarova, Institute of Biotechnology CAS, Czech Republic (Received 5 February 2018; accepted 15 February 2018; online 23 February 2018)

The title compound, C₁₅H₁₇NO₂, was synthesized in two steps from a mixture of α-himachalene (2-methylene-6,6,9-trimethylbicyclo[5.4.0^1,7]undec-8-ene), β-himachalene (2,6,6,9-tetramethylbicyclo[5.4.0^1,7]undeca-1,8-diene) and γ-himachalene (2,6,6,9-tetramethylbicyclo[5.4.0^1,7]undeca-2,8-diene), which was isolated from an essential oil of the Atlas cedar (Cedrus atlantica). The nitro group and the isopropyl group lie almost normal to the mean plane of the naphthalene moiety, making dihedral angles of 83.13 (19) and 71.72 (16)°, respectively, and are inclined to one another by 49.8 (2)°. In the crystal, molecules are linked by pairs of C—H⋯π interactions and weak C—H⋯O interactions.

Keywords: crystal structure; α-β-and γ-himachalene; Atlas cedar; C—H⋯π interactions.

CCDC reference: 1824306

Structure description

The bicyclic sesquiterpenes α-, β- and γ-himachalene are the main constituents of the essential oil of the Atlas cedar (Cedrus Atlantica) (El Haib et al., 2011 ; Loubidi et al., 2014 ). The reactivity of these sesquiterpenes and derivatives has been studied extensively by our team in order to prepare new products having biological proprieties (Zaki et al., 2014 ; Benharref et al., 2016 ; Ait Elhad et al., 2017 ). Indeed, these compounds were tested, using the food-poisoning technique, for their potential antifungal activity against the phytopathogen Botrytis cinerea (Daoubi et al., 2004 ). In this paper, we report on the crystal structure of 6-methyl-1-(nitromethyl)-4-(propan-2-yl)naphthalene.

The molecular structure of the title compound is illustrated in Fig. 1. In the molecule, the naphthalene ring system is approximately planar, with an r.m.s. deviation of 0.0156 (16) Å. The dihedral angle between the two phenyl rings is 1.11 (7)°. The nitro group (N/O1/O2) and the isopropyle group (C12/C13/C14) lie almost normal to the mean plane of the naphthalene moiety, making dihedral angles of 83.13 (19) and 71.72 (16)°, respectively, and are inclined to one another by 49.8 (2)°. In the crystal, molecules are linked by pairs of C—H⋯π interactions, forming dimers (Table 1 and Fig. 2). Two weak C10—H10⋯O1ⁱ and C11—H11A⋯O2ⁱⁱ interactions are also observed (Table 1 and Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O1ⁱ	0.95	2.49	3.349 (2)	150
C11—H11A⋯O2ⁱⁱ	0.99	2.56	3.337 (3)	135
C11—H11B⋯Cgⁱⁱ	0.99	2.91	3.511 (2)	120
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) x, y-1, z.

Figure 1
The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
A partial view of the crystal packing, showing the C—H⋯π interactions as green lines (see Table 2

; the H atom involved is shown as a blue ball).

Figure 3
A view along the b axis of the crystal packing.

Synthesis and crystallization

In a reactor of 250 ml equipped with a magnetic stirrer and a dropping funnel, we introduced 70 ml of dichloromethane and 3 ml of nitric acid. After cooling, 6 g (30 mmol) of 1-isopropyl-4,7-dimethylnaphthalene dissolved in 30 ml of dichloromethane was added dropwise through the dropping funnel (Benharref et al., 2015 ). The reaction mixture was stirred for 4 h, then 40 ml of ice water was added and the resultion solution extracted with dichloromethane. The organic layers were combined, washed three times with 40 ml with water and dried over sodium sulfate and finally concentrated under vacuum. The residue was subjected to chromatography on a silica-gel column with hexane–ethyl acetate (98/2 v/v) as eluent, which allowed the isolation of the title compound (yield: 3 g, 12 mmol, 40%). The title compound was recrystallized from hexane.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₇NO₂
M_r	243.29
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	29.001 (10), 4.8412 (19), 20.474 (9)
β (°)	113.16 (2)
V (Å³)	2642.7 (18)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.50 × 0.45 × 0.15

Data collection
Diffractometer	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.960, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	26616, 2912, 2579
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.132, 1.09
No. of reflections	2912
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.23
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS2014 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1824306

Crystal structure: contains datablocks I, block. DOI: https://doi.org/10.1107/S2414314618002742/ff4025sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618002742/ff4025Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

6-Methyl-1-(nitromethyl)-4-(propan-2-yl)naphthalene top

Crystal data top

C₁₅H₁₇NO₂	F(000) = 1040
M_r = 243.29	D_x = 1.223 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 29.001 (10) Å	Cell parameters from 2912 reflections
b = 4.8412 (19) Å	θ = 3–27.1°
c = 20.474 (9) Å	µ = 0.08 mm⁻¹
β = 113.16 (2)°	T = 173 K
V = 2642.7 (18) Å³	Plate, colourless
Z = 8	0.50 × 0.45 × 0.15 mm

Data collection top

Bruker X8 APEX diffractometer	2579 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	R_int = 0.028
φ and ω scans	θ_max = 27.1°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −36→36
T_min = 0.960, T_max = 0.988	k = −6→6
26616 measured reflections	l = −26→26
2912 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.132	w = 1/[σ²(F_o²) + (0.059P)² + 2.2975P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
2912 reflections	Δρ_max = 0.23 e Å⁻³
166 parameters	Δρ_min = −0.23 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.79689 (5)	0.2689 (3)	0.46980 (7)	0.0677 (5)
O2	0.78273 (4)	0.5935 (3)	0.39377 (7)	0.0515 (4)
N1	0.77205 (5)	0.3746 (3)	0.41311 (6)	0.0335 (3)
C11	0.72743 (6)	0.2118 (3)	0.36430 (9)	0.0374 (4)
H11A	0.7396	0.0547	0.3445	0.045*
H11B	0.7095	0.1347	0.3925	0.045*
C2	0.69125 (5)	0.3779 (3)	0.30416 (8)	0.0298 (3)
C1	0.65794 (5)	0.5709 (3)	0.31594 (7)	0.0265 (3)
C6	0.62150 (5)	0.7103 (3)	0.25662 (7)	0.0256 (3)
C5	0.61847 (5)	0.6535 (3)	0.18605 (7)	0.0274 (3)
C12	0.57701 (5)	0.7833 (3)	0.12210 (7)	0.0339 (3)
H12	0.5722	0.9767	0.1354	0.041*
C14	0.52770 (6)	0.6276 (4)	0.10593 (9)	0.0455 (4)
H14A	0.5308	0.4389	0.0908	0.068*
H14B	0.5004	0.7229	0.0679	0.068*
H14C	0.5204	0.6215	0.1487	0.068*
C3	0.68822 (5)	0.3335 (3)	0.23673 (8)	0.0344 (3)
H3	0.7108	0.2079	0.2292	0.041*
C4	0.65214 (5)	0.4710 (3)	0.17804 (7)	0.0334 (3)
H4	0.6511	0.4364	0.1318	0.040*
C7	0.58932 (5)	0.9034 (3)	0.27020 (8)	0.0307 (3)
H7	0.5649	0.9977	0.2311	0.037*
C8	0.59199 (6)	0.9594 (3)	0.33739 (8)	0.0345 (3)
C15	0.55733 (7)	1.1693 (4)	0.34918 (10)	0.0482 (4)
H15A	0.5446	1.2951	0.3084	0.072*
H15B	0.5758	1.2751	0.3924	0.072*
H15C	0.5292	1.0736	0.3543	0.072*
C9	0.62796 (6)	0.8178 (3)	0.39508 (8)	0.0387 (4)
H9	0.6301	0.8530	0.4418	0.046*
C10	0.65986 (6)	0.6305 (3)	0.38503 (8)	0.0344 (3)
H10	0.6838	0.5384	0.4250	0.041*
C13	0.58857 (7)	0.7985 (5)	0.05544 (9)	0.0549 (5)
H13A	0.6205	0.8951	0.0666	0.082*
H13B	0.5617	0.8989	0.0181	0.082*
H13C	0.5910	0.6111	0.0389	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0646 (9)	0.0796 (10)	0.0357 (6)	−0.0173 (8)	−0.0051 (6)	0.0262 (7)
O2	0.0421 (6)	0.0404 (7)	0.0567 (7)	−0.0125 (5)	0.0029 (5)	0.0166 (6)
N1	0.0311 (6)	0.0357 (7)	0.0308 (6)	−0.0003 (5)	0.0091 (5)	0.0083 (5)
C11	0.0332 (7)	0.0268 (7)	0.0435 (8)	−0.0026 (6)	0.0055 (6)	0.0102 (6)
C2	0.0267 (6)	0.0217 (6)	0.0345 (7)	−0.0027 (5)	0.0050 (5)	0.0028 (5)
C1	0.0266 (6)	0.0222 (6)	0.0285 (6)	−0.0072 (5)	0.0085 (5)	0.0007 (5)
C6	0.0259 (6)	0.0219 (6)	0.0282 (6)	−0.0040 (5)	0.0098 (5)	−0.0009 (5)
C5	0.0271 (6)	0.0273 (7)	0.0251 (6)	−0.0010 (5)	0.0075 (5)	−0.0003 (5)
C12	0.0324 (7)	0.0369 (8)	0.0282 (7)	0.0044 (6)	0.0077 (6)	0.0035 (6)
C14	0.0306 (8)	0.0500 (10)	0.0444 (9)	0.0026 (7)	0.0024 (7)	0.0018 (8)
C3	0.0294 (7)	0.0288 (7)	0.0410 (8)	0.0039 (6)	0.0096 (6)	−0.0053 (6)
C4	0.0315 (7)	0.0379 (8)	0.0285 (7)	0.0025 (6)	0.0094 (6)	−0.0063 (6)
C7	0.0306 (7)	0.0256 (7)	0.0369 (7)	−0.0019 (5)	0.0143 (6)	−0.0011 (6)
C8	0.0365 (7)	0.0303 (7)	0.0437 (8)	−0.0114 (6)	0.0231 (6)	−0.0102 (6)
C15	0.0479 (9)	0.0449 (9)	0.0650 (11)	−0.0097 (8)	0.0362 (9)	−0.0198 (8)
C9	0.0427 (8)	0.0469 (9)	0.0321 (7)	−0.0180 (7)	0.0207 (7)	−0.0104 (7)
C10	0.0347 (7)	0.0394 (8)	0.0268 (7)	−0.0115 (6)	0.0096 (6)	0.0032 (6)
C13	0.0499 (10)	0.0804 (14)	0.0309 (8)	0.0126 (10)	0.0121 (7)	0.0150 (9)

Geometric parameters (Å, º) top

O1—N1	1.2123 (17)	C14—H14B	0.9800
O2—N1	1.2133 (17)	C14—H14C	0.9800
N1—C11	1.509 (2)	C3—C4	1.412 (2)
C11—C2	1.499 (2)	C3—H3	0.9500
C11—H11A	0.9900	C4—H4	0.9500
C11—H11B	0.9900	C7—C8	1.374 (2)
C2—C3	1.365 (2)	C7—H7	0.9500
C2—C1	1.431 (2)	C8—C9	1.409 (2)
C1—C10	1.423 (2)	C8—C15	1.514 (2)
C1—C6	1.4275 (19)	C15—H15A	0.9800
C6—C7	1.4238 (19)	C15—H15B	0.9800
C6—C5	1.4389 (19)	C15—H15C	0.9800
C5—C4	1.374 (2)	C9—C10	1.367 (2)
C5—C12	1.5219 (19)	C9—H9	0.9500
C12—C13	1.530 (2)	C10—H10	0.9500
C12—C14	1.533 (2)	C13—H13A	0.9800
C12—H12	1.0000	C13—H13B	0.9800
C14—H14A	0.9800	C13—H13C	0.9800

O1—N1—O2	123.31 (14)	H14B—C14—H14C	109.5
O1—N1—C11	116.44 (13)	C2—C3—C4	121.18 (13)
O2—N1—C11	120.16 (12)	C2—C3—H3	119.4
C2—C11—N1	113.86 (12)	C4—C3—H3	119.4
C2—C11—H11A	108.8	C5—C4—C3	121.69 (13)
N1—C11—H11A	108.8	C5—C4—H4	119.2
C2—C11—H11B	108.8	C3—C4—H4	119.2
N1—C11—H11B	108.8	C8—C7—C6	122.82 (14)
H11A—C11—H11B	107.7	C8—C7—H7	118.6
C3—C2—C1	119.60 (12)	C6—C7—H7	118.6
C3—C2—C11	119.47 (14)	C7—C8—C9	118.37 (14)
C1—C2—C11	120.83 (13)	C7—C8—C15	120.83 (15)
C10—C1—C6	118.42 (13)	C9—C8—C15	120.80 (14)
C10—C1—C2	122.35 (13)	C8—C15—H15A	109.5
C6—C1—C2	119.23 (12)	C8—C15—H15B	109.5
C7—C6—C1	117.85 (12)	H15A—C15—H15B	109.5
C7—C6—C5	122.40 (12)	C8—C15—H15C	109.5
C1—C6—C5	119.75 (12)	H15A—C15—H15C	109.5
C4—C5—C6	118.51 (12)	H15B—C15—H15C	109.5
C4—C5—C12	121.39 (12)	C10—C9—C8	121.21 (13)
C6—C5—C12	120.03 (12)	C10—C9—H9	119.4
C5—C12—C13	114.28 (13)	C8—C9—H9	119.4
C5—C12—C14	109.69 (13)	C9—C10—C1	121.33 (14)
C13—C12—C14	110.13 (14)	C9—C10—H10	119.3
C5—C12—H12	107.5	C1—C10—H10	119.3
C13—C12—H12	107.5	C12—C13—H13A	109.5
C14—C12—H12	107.5	C12—C13—H13B	109.5
C12—C14—H14A	109.5	H13A—C13—H13B	109.5
C12—C14—H14B	109.5	C12—C13—H13C	109.5
H14A—C14—H14B	109.5	H13A—C13—H13C	109.5
C12—C14—H14C	109.5	H13B—C13—H13C	109.5
H14A—C14—H14C	109.5

O1—N1—C11—C2	165.52 (15)	C6—C5—C12—C13	158.16 (15)
O2—N1—C11—C2	−17.5 (2)	C4—C5—C12—C14	99.23 (17)
N1—C11—C2—C3	108.31 (16)	C6—C5—C12—C14	−77.62 (17)
N1—C11—C2—C1	−75.26 (17)	C1—C2—C3—C4	−1.2 (2)
C3—C2—C1—C10	−178.70 (13)	C11—C2—C3—C4	175.32 (13)
C11—C2—C1—C10	4.87 (19)	C6—C5—C4—C3	1.9 (2)
C3—C2—C1—C6	1.04 (19)	C12—C5—C4—C3	−175.00 (13)
C11—C2—C1—C6	−175.39 (12)	C2—C3—C4—C5	−0.3 (2)
C10—C1—C6—C7	0.49 (18)	C1—C6—C7—C8	−0.1 (2)
C2—C1—C6—C7	−179.26 (12)	C5—C6—C7—C8	−179.87 (13)
C10—C1—C6—C5	−179.72 (12)	C6—C7—C8—C9	−0.4 (2)
C2—C1—C6—C5	0.53 (18)	C6—C7—C8—C15	179.23 (13)
C7—C6—C5—C4	177.81 (13)	C7—C8—C9—C10	0.5 (2)
C1—C6—C5—C4	−1.97 (19)	C15—C8—C9—C10	−179.12 (14)
C7—C6—C5—C12	−5.24 (19)	C8—C9—C10—C1	−0.1 (2)
C1—C6—C5—C12	174.98 (12)	C6—C1—C10—C9	−0.4 (2)
C4—C5—C12—C13	−25.0 (2)	C2—C1—C10—C9	179.35 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1ⁱ	0.95	2.49	3.349 (2)	150
C11—H11A···O2ⁱⁱ	0.99	2.56	3.337 (3)	135
C11—H11B···Cgⁱⁱ	0.99	2.91	3.511 (2)	120

Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) x, y−1, z.

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

References

Ait Elhad, M., Benharref, A., Taourirte, M., Daran J-Cl Oukhrib, A. & Berraho, M. (2017). IUCrData, 2, x170368. Google Scholar
Benharref, A., Elkarroumi, J., El Ammari, L., Saadi, M. & Berraho, M. (2015). Acta Cryst. E71, o659–o660. Web of Science CSD CrossRef IUCr Journals Google Scholar
Benharref, A., Oukhrib, A., Ait Elhad, M., El Ammari, L., Saadi, M. & Berraho, M. (2016). IUCrData, 1, x160703. Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Daoubi, M., Duran-Patron, R., Hmamouchi, M., Hernandez-Galan, R., Benharref, A. & Isidro, G. C. (2004). Pest Manag. Sci. 60, 927–932. Web of Science CrossRef PubMed CAS Google Scholar
El Haib, A., Benharref, A., Parrès-Maynadié, S., Manoury, E., Urrutigoïty, M. & Gouygou, M. (2011). Tetrahedron Asymmetry, 22, 101–108. Web of Science CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Loubidi, M., Agustin, D., Benharref, A. & Poli, R. (2014). C. R. Chim. 17, 549–556. Web of Science CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zaki, M., Benharref, A., El Ammari, L., Saadi, M. & Berraho, M. (2014). Acta Cryst. E70, o444. CSD CrossRef 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.