2-Isopropyl-4,7-dimethyl-1-nitro­naphthalene

Benharref, A.; El Ammari, L.; Saadi, M.; Mazoir, N.; Daran, J.-C.; Berraho, M.

doi:10.1107/S2414314617005843

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 4| April 2017| x170584

https://doi.org/10.1107/S2414314617005843

Open

access

2-Isopropyl-4,7-dimethyl-1-nitronaphthalene

Ahmed Benharref,^a ^* Lahcen El Ammari,^b Mohamed Saadi,^b Noureddine Mazoir,^a Jean-Claude Daran ^c 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, ^bLaboratoire de Chimie du Solide Appliqué, Faculté des Sciences, Mohammed V University in Rabat, Avenue Ibn Battouta BP 1014 Rabat, Morocco, and ^cLaboratoire de Chimie de Coordination, 205 route de Narbonne, 31077 Toulouse Cedex 04, France
^*Correspondence e-mail: benharref@uca.ac.ma

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 7 April 2017; accepted 19 April 2017; online 28 April 2017)

All the non-H atoms of the title compound, C₁₅H₁₇NO₂, except the CH₃ groups of the isopropyl unit and the O atoms of the nitro group, lie on a crystallographic mirror plane. The dihedral angle between the naphthalene plane and the nitro group is constrained to be 90° by symmetry. In the crystal, molecules are linked by π–π interactions [centroid–centroid separation = 3.6591 (4) Å] and stacked along the b-axis direction.

Keywords: crystal structure; β-himachalene; π–π interaction.

CCDC reference: 1544812

Structure description

The bicyclic sesquiterpenes α- and β-himachalene are the main constituents of the essential oil of the Atlas cedar (Cedrus atlantica) (Benharref et al., 2015 ; Loubidi et al., 2014 ). As part of our ongoing studies of such systems (Benharref et al., 2016 ), we now report the synthesis and crystal structure of the title compound.

The molecular structure of the title compound is illustrated in Fig. 1. The naphthalene ring system is perfectly planar (all atoms lie on a crystallographic mirror plane). The O atom of the nitro group (N1/O1/O1a) and the isopropyl group (C13/C13a) lie perfectly normal to the mean plane of the naphthalene moieties with the same dihedral angle of 90°. In the crystal, molecules are linked through π–π interactions between naphthalene ring systems stacked along b axis, as shown in Fig. 2, the intercentroid distance being 3.6591 (4) Å.

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. Atoms with suffix `a' are generated by the symmetry operation (x, $[{3\over 2}]$ − y, z).

Figure 2
Crystal packing of the title compound, showing intermolecular π–π interactions between naphthalene ring systems (dashed green line).

Synthesis and crystallization

In a reactor of 250 ml volume equipped with a magnetic stirrer and a dropping funnel, were introduced 60 ml of dichloromethane, 3 ml of nitric acid and 5 ml of concentrated sulfuric acid. After cooling, 6 g (30 mmol) of 2-isopropyl-4,7-dimethylnaphthalene, which was synthesized from a mixture of α and β himachalene (Benharref et al. 2016), dissolved in 30 ml of dichloromethane was added dropwise through the dropping funnel. The reaction mixture was stirred for 4 h, then quenched with 50 ml of water ice and extracted with dichloromethane. The organic layers were combined, washed five times with 40 ml with water and dried over sodium sulfate and then concentrated under vacuum. Chromatography on a silica gel column of the residue with hexane–ethyl acetate (98/2) as eluent of the residue gave the title compound (yield 5 g, 66%; 20 mmol). It was recrystallized from cyclohexane solution to obtain yellow blocks.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₅H₁₇NO₂
M_r	243.29
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	173
a, b, c (Å)	15.6744 (12), 6.9475 (5), 11.9880 (8)
V (Å³)	1305.47 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.48 × 0.20 × 0.15

Data collection
Diffractometer	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.811, 1.0
No. of measured, independent and observed [I > 2σ(I)] reflections	7047, 1344, 1155
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.110, 1.06
No. of reflections	1344
No. of parameters	107
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.32
Computer programs: APEX2 and 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: 1544812

Crystal structure: contains datablocks I, block. DOI: https://doi.org/10.1107/S2414314617005843/hb4139sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617005843/hb4139Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617005843/hb4139Isup3.cml

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).

2-Isopropyl-4,7-dimethyl-1-nitronaphthalene top

Crystal data top

C₁₅H₁₇NO₂	D_x = 1.238 Mg m⁻³
M_r = 243.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 7047 reflections
a = 15.6744 (12) Å	θ = 3.4–25.7°
b = 6.9475 (5) Å	µ = 0.08 mm⁻¹
c = 11.9880 (8) Å	T = 173 K
V = 1305.47 (16) Å³	Box, yellow
Z = 4	0.48 × 0.20 × 0.15 mm
F(000) = 520

Data collection top

Bruker X8 APEX diffractometer	1155 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	R_int = 0.017
φ and ω scans	θ_max = 25.7°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −18→19
T_min = 0.811, T_max = 1.0	k = −8→8
7047 measured reflections	l = −14→12
1344 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.040	w = 1/[σ²(F_o²) + (0.0484P)² + 0.5331P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.110	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.22 e Å⁻³
1344 reflections	Δρ_min = −0.32 e Å⁻³
107 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.010 (2)

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	Occ. (<1)
C1	0.45971 (10)	0.7500	0.51511 (14)	0.0202 (4)
C2	0.37870 (10)	0.7500	0.56986 (14)	0.0223 (4)
C3	0.37553 (10)	0.7500	0.68398 (15)	0.0240 (4)
H3	0.3213	0.7500	0.7194	0.029*
C4	0.44979 (11)	0.7500	0.75165 (15)	0.0235 (4)
C5	0.52612 (10)	0.7500	0.69686 (14)	0.0219 (4)
C6	0.53587 (10)	0.7500	0.57949 (14)	0.0203 (4)
C7	0.61626 (11)	0.7500	0.52544 (15)	0.0243 (4)
H7	0.6668	0.7500	0.5692	0.029*
C8	0.62275 (11)	0.7500	0.41138 (15)	0.0263 (4)
C9	0.54670 (12)	0.7500	0.34848 (15)	0.0274 (4)
H9	0.5502	0.7500	0.2694	0.033*
C10	0.46828 (11)	0.7500	0.39775 (15)	0.0243 (4)
H10	0.4186	0.7500	0.3524	0.029*
C11	0.29772 (11)	0.7500	0.50229 (16)	0.0304 (4)
H11A	0.2914	0.8743	0.4645	0.046*	0.5
H11B	0.2488	0.7289	0.5518	0.046*	0.5
H11C	0.3002	0.6468	0.4466	0.046*	0.5
C12	0.44162 (12)	0.7500	0.87820 (14)	0.0296 (4)
H12	0.5005	0.7500	0.9102	0.035*
C13	0.39654 (12)	0.5696 (2)	0.91927 (12)	0.0503 (5)
H13A	0.3924	0.5730	1.0008	0.076*
H13B	0.4290	0.4557	0.8964	0.076*
H13C	0.3391	0.5637	0.8871	0.076*
C15	0.70823 (12)	0.7500	0.35406 (17)	0.0360 (5)
H15A	0.7247	0.6174	0.3365	0.054*	0.5
H15B	0.7510	0.8076	0.4034	0.054*	0.5
H15C	0.7046	0.8250	0.2850	0.054*	0.5
N1	0.60582 (9)	0.7500	0.76224 (12)	0.0291 (4)
O1	0.63733 (8)	0.90193 (18)	0.78734 (12)	0.0710 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0220 (9)	0.0144 (7)	0.0243 (8)	0.000	−0.0010 (6)	0.000
C2	0.0202 (8)	0.0168 (8)	0.0299 (9)	0.000	−0.0016 (7)	0.000
C3	0.0205 (8)	0.0222 (8)	0.0292 (9)	0.000	0.0038 (7)	0.000
C4	0.0262 (9)	0.0200 (8)	0.0241 (8)	0.000	0.0003 (7)	0.000
C5	0.0214 (8)	0.0196 (8)	0.0246 (9)	0.000	−0.0041 (7)	0.000
C6	0.0211 (8)	0.0141 (8)	0.0258 (9)	0.000	−0.0005 (6)	0.000
C7	0.0208 (8)	0.0206 (8)	0.0316 (9)	0.000	−0.0009 (7)	0.000
C8	0.0277 (9)	0.0188 (8)	0.0325 (9)	0.000	0.0064 (7)	0.000
C9	0.0353 (10)	0.0242 (9)	0.0229 (8)	0.000	0.0041 (7)	0.000
C10	0.0271 (9)	0.0214 (8)	0.0243 (9)	0.000	−0.0031 (7)	0.000
C11	0.0223 (9)	0.0349 (10)	0.0338 (10)	0.000	−0.0036 (7)	0.000
C12	0.0302 (9)	0.0358 (10)	0.0227 (9)	0.000	0.0021 (7)	0.000
C13	0.0738 (11)	0.0473 (9)	0.0299 (7)	−0.0109 (8)	0.0101 (7)	0.0065 (7)
C15	0.0310 (10)	0.0371 (11)	0.0400 (11)	0.000	0.0110 (8)	0.000
N1	0.0252 (8)	0.0363 (9)	0.0257 (8)	0.000	−0.0033 (6)	0.000
O1	0.0669 (9)	0.0493 (7)	0.0967 (10)	−0.0205 (6)	−0.0519 (7)	0.0045 (7)

Geometric parameters (Å, º) top

C1—C10	1.413 (2)	C9—H9	0.9500
C1—C6	1.422 (2)	C10—H10	0.9500
C1—C2	1.429 (2)	C11—H11A	0.9800
C2—C3	1.369 (2)	C11—H11B	0.9800
C2—C11	1.506 (2)	C11—H11C	0.9800
C3—C4	1.419 (2)	C12—C13ⁱ	1.5208 (18)
C3—H3	0.9500	C12—C13	1.5209 (18)
C4—C5	1.365 (2)	C12—H12	1.0000
C4—C12	1.523 (2)	C13—H13A	0.9800
C5—C6	1.415 (2)	C13—H13B	0.9800
C5—N1	1.475 (2)	C13—H13C	0.9800
C6—C7	1.417 (2)	C15—H15A	0.9800
C7—C8	1.371 (3)	C15—H15B	0.9800
C7—H7	0.9500	C15—H15C	0.9800
C8—C9	1.410 (3)	N1—O1	1.2035 (13)
C8—C15	1.506 (2)	N1—O1ⁱ	1.2036 (13)
C9—C10	1.364 (2)

C10—C1—C6	117.43 (15)	C1—C10—H10	119.4
C10—C1—C2	122.79 (15)	C2—C11—H11A	109.5
C6—C1—C2	119.78 (15)	C2—C11—H11B	109.5
C3—C2—C1	119.42 (15)	H11A—C11—H11B	109.5
C3—C2—C11	120.47 (15)	C2—C11—H11C	109.5
C1—C2—C11	120.12 (15)	H11A—C11—H11C	109.5
C2—C3—C4	122.79 (15)	H11B—C11—H11C	109.5
C2—C3—H3	118.6	C13ⁱ—C12—C13	111.02 (17)
C4—C3—H3	118.6	C13ⁱ—C12—C4	111.20 (10)
C5—C4—C3	116.35 (16)	C13—C12—C4	111.20 (10)
C5—C4—C12	123.60 (16)	C13ⁱ—C12—H12	107.7
C3—C4—C12	120.05 (15)	C13—C12—H12	107.7
C4—C5—C6	124.97 (15)	C4—C12—H12	107.7
C4—C5—N1	119.13 (15)	C12—C13—H13A	109.5
C6—C5—N1	115.90 (14)	C12—C13—H13B	109.5
C5—C6—C7	123.42 (15)	H13A—C13—H13B	109.5
C5—C6—C1	116.68 (14)	C12—C13—H13C	109.5
C7—C6—C1	119.90 (15)	H13A—C13—H13C	109.5
C8—C7—C6	121.47 (16)	H13B—C13—H13C	109.5
C8—C7—H7	119.3	C8—C15—H15A	109.5
C6—C7—H7	119.3	C8—C15—H15B	109.5
C7—C8—C9	118.06 (16)	H15A—C15—H15B	109.5
C7—C8—C15	121.40 (17)	C8—C15—H15C	109.5
C9—C8—C15	120.53 (16)	H15A—C15—H15C	109.5
C10—C9—C8	122.02 (16)	H15B—C15—H15C	109.5
C10—C9—H9	119.0	O1—N1—O1ⁱ	122.57 (16)
C8—C9—H9	119.0	O1—N1—C5	118.71 (8)
C9—C10—C1	121.12 (16)	O1ⁱ—N1—C5	118.71 (8)
C9—C10—H10	119.4

Symmetry code: (i) x, −y+3/2, z.

Acknowledgements

The authors thank the Laboratoire de Chimie de Coordination, UPR-CNRS 8241 Toulouse, for the X-ray measurements.

References

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
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

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.