organic compounds
1-(7-Isopropyl-2,5-dimethyl-8-nitronaphthalen-1-yl)ethanone
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 Bioorganique et Macromoléculaire, Faculté des Sciences et Techniques, Université Cadi Ayyad, 40000 Marrakech, Morocco, and cLaboratoire de Chimie de Coordination, 205 route de Narbonne, 31077 Toulouse Cedex 04, France
*Correspondence e-mail: aitelhad2017@gmail.com
The title compound, C17H19NO3, was synthesized in three steps from a mixture of α-, β- and γ-himachalene, which was isolated from an essential oil of the Atlas cedar (Cedrus atlantica). The dihedral angle between the two rings of the naphthalene moiety is 2.54 (5)°. The nitro group and the acetyl group lie almost normal to the mean plane of the naphthalene moiety, making dihedral angles of 80.29 (13) and 83.01 (15)°, respectively, and are inclined to one another by 13.23 (19)°. There is an intramolecular C—H⋯O hydrogen bond present involving a nitro O atom and the H atom of the methine C atom of the isopropyl group, forming an S(6) ring motif. In the crystal, molecules are linked by pairs of C—H⋯π interactions, forming inversion dimers. There are no other significant intermolecular interactions present.
Keywords: crystal structure; β-himachalene; Atlas cedar; hydrogen bonding.
CCDC reference: 1536512
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). The reactivity of these sesquiterpenes and their derivatives have been studied extensively by our team in order to prepare new products having biological proprieties (El Haib et al., 2011; Benharref et al., 2013, 2015, 2016; Zaki et al., 2014). Indeed, these compounds have been tested, using the food poisoning technique, for their potential antifungal activity against the phytopathogen Botrytis cinerea (Daoubi et al., 2004). Herein, we report on the of the title compound.
The molecular structure of the title compound is illustrated in Fig. 1. The naphthalene ring system is approximately planar, with the dihedral angle between the two benzene rings being 2.54 (5)°. The nitro group (N1/O21/O22) and the acteyl group (C11/O11/C12) lie almost normal to the mean plane of the naphthalene moiety, making dihedral angles of 80.29 (13) and 83.01 (15)°, respectively, and are inclined to one another by 13.23 (19)°. There is an intramolecular C—H⋯O hydrogen bond present involving a nitro O atom, O21, and the H atom of atom C13 of the isopropyl group, forming an S(6) ring motif (Table 1 and Fig. 1).
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In the crystal, molecules are linked by pairs of C—H⋯π interactions, forming inversion dimers (Table 1 and Fig. 2). There are no other significant intermolecular interactions present.
Synthesis and crystallization
In a 250 ml reactor 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 1,6-dimethyl-4-isopropylnaphtalene (Benharref et al., 2016) dissolved in 30 ml of dichloromethane were added dropwise through a dropping funnel. The reaction mixture was stirred for 4 h, then 50 ml of ice–water were added and the mixture was extracted with dichloromethane. The organic layers were combined, washed with water (5 × 40 ml) and dried over sodium sulfate and then concentrated in vacuo. The residue was subjected to on a column of silica gel with hexane–ethyl acetate (98:2) as to obtain 5 g (20 mmol) of 2-isopropyl-4,7-dimethyl-1-nitronaphthalene. 3 g (10 mmol) of the latter compound were treated with two equivalents of acetyl chloride in the presence of 2 equivalents of aluminium chloride in 50 ml of dichloromethane with stirring at room temperature for 6 h. After addition of 30 ml of water, the reaction mixture was extracted with dichloromethane (3 × 20 ml). The organic phases were combined, dried over sodium sulfate and then concentrated in vacuo. on a silica gel column with hexane–ethyl acetate (97:3) as of the residue gave the title compound (yield 1.5 g, 6 mmol; 60%). It was recrystallized from cyclohexane to obtain colourless plate-like crystals.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1536512
https://doi.org/10.1107/S2414314617003686/su4136sup1.cif
contains datablocks I, block. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617003686/su4136Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617003686/su4136Isup3.cml
Data collection: APEX2 (Bruker, 2009); cell
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).C17H19NO3 | F(000) = 608 |
Mr = 285.33 | Dx = 1.289 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.8570 (5) Å | Cell parameters from 3005 reflections |
b = 9.0549 (4) Å | θ = 3.2–26.4° |
c = 14.9550 (7) Å | µ = 0.09 mm−1 |
β = 91.006 (4)° | T = 173 K |
V = 1469.99 (12) Å3 | Plate, colourless |
Z = 4 | 0.50 × 0.45 × 0.15 mm |
Bruker X8 APEX diffractometer | 3005 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 2548 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
φ and ω scans | θmax = 26.4°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −13→13 |
Tmin = 0.811, Tmax = 1.0 | k = −11→11 |
15373 measured reflections | l = −18→18 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0501P)2 + 0.4513P] where P = (Fo2 + 2Fc2)/3 |
3005 reflections | (Δ/σ)max < 0.001 |
194 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O11 | 0.18310 (9) | 0.30707 (12) | 0.51378 (7) | 0.0414 (3) | |
O21 | 0.31296 (9) | 0.05669 (11) | 0.42478 (7) | 0.0397 (3) | |
O22 | 0.46037 (9) | 0.16464 (11) | 0.49836 (6) | 0.0387 (3) | |
N1 | 0.39471 (10) | 0.14874 (11) | 0.43175 (7) | 0.0256 (2) | |
C1 | 0.37364 (10) | 0.39248 (13) | 0.35320 (7) | 0.0198 (2) | |
C2 | 0.41980 (10) | 0.24493 (13) | 0.35431 (8) | 0.0210 (3) | |
C3 | 0.49041 (11) | 0.18396 (13) | 0.28881 (8) | 0.0232 (3) | |
C4 | 0.51874 (11) | 0.27486 (14) | 0.21482 (8) | 0.0246 (3) | |
H4 | 0.5702 | 0.2364 | 0.1696 | 0.030* | |
C5 | 0.47494 (10) | 0.41555 (13) | 0.20598 (8) | 0.0224 (3) | |
C6 | 0.40118 (10) | 0.47684 (13) | 0.27500 (8) | 0.0207 (3) | |
C7 | 0.35676 (11) | 0.62331 (14) | 0.26845 (8) | 0.0246 (3) | |
H7 | 0.3725 | 0.6791 | 0.2161 | 0.030* | |
C8 | 0.29211 (12) | 0.68594 (14) | 0.33537 (9) | 0.0278 (3) | |
H8 | 0.2649 | 0.7852 | 0.3294 | 0.033* | |
C9 | 0.26449 (11) | 0.60652 (14) | 0.41374 (8) | 0.0261 (3) | |
C10 | 0.30488 (10) | 0.46193 (13) | 0.42254 (8) | 0.0219 (3) | |
C11 | 0.27223 (11) | 0.38588 (14) | 0.50948 (8) | 0.0258 (3) | |
C12 | 0.35266 (14) | 0.41952 (18) | 0.58950 (9) | 0.0386 (3) | |
H12A | 0.3426 | 0.5234 | 0.6063 | 0.058* | |
H12B | 0.4389 | 0.4010 | 0.5749 | 0.058* | |
H12C | 0.3290 | 0.3562 | 0.6395 | 0.058* | |
C13 | 0.54302 (12) | 0.02859 (14) | 0.29434 (9) | 0.0275 (3) | |
H13 | 0.4955 | −0.0276 | 0.3398 | 0.033* | |
C14 | 0.67745 (13) | 0.03500 (17) | 0.32595 (11) | 0.0409 (4) | |
H14A | 0.7243 | 0.0975 | 0.2852 | 0.061* | |
H14B | 0.7122 | −0.0649 | 0.3265 | 0.061* | |
H14C | 0.6821 | 0.0765 | 0.3864 | 0.061* | |
C15 | 0.53056 (15) | −0.05265 (16) | 0.20523 (10) | 0.0393 (3) | |
H15A | 0.4438 | −0.0545 | 0.1861 | 0.059* | |
H15B | 0.5608 | −0.1540 | 0.2123 | 0.059* | |
H32B | 0.5791 | −0.0015 | 0.1601 | 0.059* | |
C16 | 0.50429 (12) | 0.50419 (15) | 0.12365 (8) | 0.0284 (3) | |
H16A | 0.5556 | 0.4450 | 0.0840 | 0.043* | |
H16B | 0.5488 | 0.5941 | 0.1412 | 0.043* | |
H16C | 0.4275 | 0.5310 | 0.0922 | 0.043* | |
C17 | 0.18716 (14) | 0.68217 (17) | 0.48318 (10) | 0.0384 (3) | |
H17A | 0.1689 | 0.7834 | 0.4639 | 0.058* | 0.5 |
H17B | 0.1099 | 0.6277 | 0.4903 | 0.058* | 0.5 |
H17C | 0.2325 | 0.6845 | 0.5404 | 0.058* | 0.5 |
H17D | 0.1720 | 0.6137 | 0.5325 | 0.058* | 0.5 |
H17E | 0.2309 | 0.7693 | 0.5061 | 0.058* | 0.5 |
H17F | 0.1084 | 0.7126 | 0.4560 | 0.058* | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
O11 | 0.0335 (5) | 0.0469 (6) | 0.0440 (6) | −0.0094 (5) | 0.0081 (4) | 0.0083 (5) |
O21 | 0.0422 (6) | 0.0355 (5) | 0.0417 (6) | −0.0116 (4) | 0.0097 (4) | 0.0077 (4) |
O22 | 0.0480 (6) | 0.0449 (6) | 0.0229 (5) | 0.0056 (5) | −0.0055 (4) | 0.0064 (4) |
N1 | 0.0289 (5) | 0.0240 (5) | 0.0240 (6) | 0.0035 (4) | 0.0048 (4) | 0.0041 (4) |
C1 | 0.0177 (5) | 0.0231 (6) | 0.0186 (6) | −0.0035 (4) | −0.0015 (4) | 0.0003 (5) |
C2 | 0.0206 (5) | 0.0237 (6) | 0.0186 (6) | −0.0029 (4) | 0.0003 (4) | 0.0036 (5) |
C3 | 0.0220 (5) | 0.0241 (6) | 0.0236 (6) | −0.0005 (5) | 0.0017 (4) | 0.0010 (5) |
C4 | 0.0240 (6) | 0.0284 (6) | 0.0215 (6) | −0.0003 (5) | 0.0058 (4) | 0.0001 (5) |
C5 | 0.0211 (6) | 0.0270 (6) | 0.0192 (6) | −0.0043 (5) | 0.0005 (4) | 0.0024 (5) |
C6 | 0.0194 (5) | 0.0238 (6) | 0.0188 (6) | −0.0033 (4) | −0.0022 (4) | 0.0012 (5) |
C7 | 0.0246 (6) | 0.0252 (6) | 0.0239 (6) | −0.0022 (5) | −0.0015 (5) | 0.0052 (5) |
C8 | 0.0300 (6) | 0.0233 (6) | 0.0302 (7) | 0.0025 (5) | −0.0020 (5) | 0.0017 (5) |
C9 | 0.0260 (6) | 0.0278 (6) | 0.0245 (6) | 0.0006 (5) | −0.0003 (5) | −0.0022 (5) |
C10 | 0.0199 (5) | 0.0263 (6) | 0.0196 (6) | −0.0021 (5) | −0.0010 (4) | −0.0003 (5) |
C11 | 0.0249 (6) | 0.0272 (6) | 0.0255 (7) | 0.0033 (5) | 0.0073 (5) | 0.0001 (5) |
C12 | 0.0464 (8) | 0.0473 (9) | 0.0220 (7) | 0.0026 (7) | 0.0002 (6) | 0.0008 (6) |
C13 | 0.0295 (6) | 0.0253 (6) | 0.0280 (7) | 0.0028 (5) | 0.0070 (5) | 0.0036 (5) |
C14 | 0.0346 (7) | 0.0393 (8) | 0.0486 (9) | 0.0084 (6) | −0.0028 (6) | 0.0014 (7) |
C15 | 0.0502 (9) | 0.0266 (7) | 0.0411 (8) | 0.0005 (6) | 0.0036 (7) | −0.0030 (6) |
C16 | 0.0317 (6) | 0.0321 (7) | 0.0215 (6) | −0.0009 (5) | 0.0050 (5) | 0.0052 (5) |
C17 | 0.0482 (8) | 0.0353 (8) | 0.0320 (8) | 0.0107 (6) | 0.0074 (6) | −0.0030 (6) |
O11—C11 | 1.2050 (16) | C11—C12 | 1.5002 (19) |
O21—N1 | 1.2206 (14) | C12—H12A | 0.9800 |
O22—N1 | 1.2232 (14) | C12—H12B | 0.9800 |
N1—C2 | 1.4783 (15) | C12—H12C | 0.9800 |
C1—C2 | 1.4269 (16) | C13—C15 | 1.5261 (19) |
C1—C6 | 1.4327 (16) | C13—C14 | 1.5273 (19) |
C1—C10 | 1.4337 (16) | C13—H13 | 1.0000 |
C2—C3 | 1.3706 (17) | C14—H14A | 0.9800 |
C3—C4 | 1.4172 (17) | C14—H14B | 0.9800 |
C3—C13 | 1.5201 (17) | C14—H14C | 0.9800 |
C4—C5 | 1.3654 (18) | C15—H15A | 0.9800 |
C4—H4 | 0.9500 | C15—H15B | 0.9800 |
C5—C6 | 1.4295 (17) | C15—H32B | 0.9800 |
C5—C16 | 1.5085 (17) | C16—H16A | 0.9800 |
C6—C7 | 1.4141 (17) | C16—H16B | 0.9800 |
C7—C8 | 1.3567 (18) | C16—H16C | 0.9800 |
C7—H7 | 0.9500 | C17—H17A | 0.9800 |
C8—C9 | 1.4118 (18) | C17—H17B | 0.9800 |
C8—H8 | 0.9500 | C17—H17C | 0.9800 |
C9—C10 | 1.3862 (18) | C17—H17D | 0.9800 |
C9—C17 | 1.5110 (18) | C17—H17E | 0.9800 |
C10—C11 | 1.5187 (17) | C17—H17F | 0.9800 |
O21—N1—O22 | 124.23 (11) | C15—C13—C14 | 110.99 (12) |
O21—N1—C2 | 118.63 (10) | C3—C13—H13 | 108.1 |
O22—N1—C2 | 117.12 (10) | C15—C13—H13 | 108.1 |
C2—C1—C6 | 115.50 (10) | C14—C13—H13 | 108.1 |
C2—C1—C10 | 126.12 (10) | C13—C14—H14A | 109.5 |
C6—C1—C10 | 118.38 (10) | C13—C14—H14B | 109.5 |
C3—C2—C1 | 124.71 (11) | H14A—C14—H14B | 109.5 |
C3—C2—N1 | 115.83 (10) | C13—C14—H14C | 109.5 |
C1—C2—N1 | 119.43 (10) | H14A—C14—H14C | 109.5 |
C2—C3—C4 | 117.12 (11) | H14B—C14—H14C | 109.5 |
C2—C3—C13 | 123.25 (11) | C13—C15—H15A | 109.5 |
C4—C3—C13 | 119.57 (11) | C13—C15—H15B | 109.5 |
C5—C4—C3 | 122.51 (11) | H15A—C15—H15B | 109.5 |
C5—C4—H4 | 118.7 | C13—C15—H32B | 109.5 |
C3—C4—H4 | 118.7 | H15A—C15—H32B | 109.5 |
C4—C5—C6 | 119.40 (11) | H15B—C15—H32B | 109.5 |
C4—C5—C16 | 119.81 (11) | C5—C16—H16A | 109.5 |
C6—C5—C16 | 120.78 (11) | C5—C16—H16B | 109.5 |
C7—C6—C5 | 120.58 (11) | H16A—C16—H16B | 109.5 |
C7—C6—C1 | 118.74 (11) | C5—C16—H16C | 109.5 |
C5—C6—C1 | 120.66 (11) | H16A—C16—H16C | 109.5 |
C8—C7—C6 | 121.41 (11) | H16B—C16—H16C | 109.5 |
C8—C7—H7 | 119.3 | C9—C17—H17A | 109.5 |
C6—C7—H7 | 119.3 | C9—C17—H17B | 109.5 |
C7—C8—C9 | 121.31 (12) | H17A—C17—H17B | 109.5 |
C7—C8—H8 | 119.3 | C9—C17—H17C | 109.5 |
C9—C8—H8 | 119.3 | H17A—C17—H17C | 109.5 |
C10—C9—C8 | 119.24 (11) | H17B—C17—H17C | 109.5 |
C10—C9—C17 | 122.80 (12) | C9—C17—H17D | 109.5 |
C8—C9—C17 | 117.92 (12) | H17A—C17—H17D | 141.1 |
C9—C10—C1 | 120.90 (11) | H17B—C17—H17D | 56.3 |
C9—C10—C11 | 115.55 (11) | H17C—C17—H17D | 56.3 |
C1—C10—C11 | 123.55 (10) | C9—C17—H17E | 109.5 |
O11—C11—C12 | 122.30 (12) | H17A—C17—H17E | 56.3 |
O11—C11—C10 | 120.93 (12) | H17B—C17—H17E | 141.1 |
C12—C11—C10 | 116.72 (11) | H17C—C17—H17E | 56.3 |
C11—C12—H12A | 109.5 | H17D—C17—H17E | 109.5 |
C11—C12—H12B | 109.5 | C9—C17—H17F | 109.5 |
H12A—C12—H12B | 109.5 | H17A—C17—H17F | 56.3 |
C11—C12—H12C | 109.5 | H17B—C17—H17F | 56.3 |
H12A—C12—H12C | 109.5 | H17C—C17—H17F | 141.1 |
H12B—C12—H12C | 109.5 | H17D—C17—H17F | 109.5 |
C3—C13—C15 | 111.78 (11) | H17E—C17—H17F | 109.5 |
C3—C13—C14 | 109.74 (11) |
Cg is the centroid of the C1/C6–C10 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···O21 | 1.00 | 2.49 | 3.2063 (16) | 128 |
C12—H12B···Cgi | 0.98 | 2.79 | 3.562 (2) | 136 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
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., Mazoir, N., Daran, J.-C. & Berraho, M. (2013). Acta Cryst. E69, o1777–o1778. 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., Durán-Patrón, R., Hmamouchi, M., Hernández-Galán, R., Benharref, A. & Collado, I. G. (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
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