N-(4-Methyl­benz­yl)-3-nitro­aniline

Marijana Đaković; Tomislav Portada; Tin Klačić

doi:10.1107/S1600536812024348

. 2012 May 31;68(Pt 6):o1967. doi: 10.1107/S1600536812024348

N-(4-Methylbenzyl)-3-nitroaniline

Marijana Đaković ^a,^*, Tomislav Portada ^b, Tin Klačić ^c

PMCID: PMC3379515 PMID: 22719713

Abstract

In the title compound, C₁₄H₁₄N₂O₂, the angle between the mean plane of the N-methyl-3-nitroaniline system (r.m.s. deviation = 0.0185 Å) and the p-tolyl unit is 89.79 (4)°. In the crystal, hydrogen-bonded chains running along [10-1] are generated by the linking of neighbouring molecules via N—H⋯O and C—H⋯O hydrogen bonds involving the 3-nitroaniline systems and forming R ₂ ²(8) motifs.

Related literature

For related structures, see: Betz et al. (2011 ▶); Stilinović & Portada (2011 ▶); Xing et al. (2006 ▶). For the synthesis, see: Magyarfalvi (2008 ▶). For graph-set theory, see: Etter (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₄H₁₄N₂O₂
M _r = 242.27
Monoclinic,
a = 5.1851 (4) Å
b = 21.408 (2) Å
c = 5.6833 (4) Å
β = 98.010 (7)°
V = 624.71 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.57 × 0.50 × 0.19 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire-3 CCD area detector
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.953, T _max = 0.958
11868 measured reflections
1856 independent reflections
1373 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.117
S = 1.03
1856 reflections
167 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812024348/fj2555sup1.cif

e-68-o1967-sup1.cif^{(23.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024348/fj2555Isup2.hkl

e-68-o1967-Isup2.hkl^{(89.5KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2ⁱ	0.78 (3)	2.52 (3)	3.277 (3)	168 (3)
C6—H6⋯O1ⁱ	0.93	2.44	3.364 (3)	171
C7—H7A⋯O2ⁱⁱ	0.97	2.64	3.352 (3)	130
C13—H13⋯O2ⁱⁱⁱ	0.93	2.69	3.282 (4)	122

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

This research was supported by the Ministry of Science, Education and Sports of the Republic of Croatia, Zagreb (grant Nos. 119–1193079–1332 and 098–0982904–2912) and the 5th High School, Zagreb, Croatia.

supplementary crystallographic information

Comment

The title compound, N-(4-methylbenzyl)-3-nitroaniline, is prepared as a part of the laboratory work with high school students, and the synthesis followed the Preparatory problems for the 40th International Chemistry Olympiad (Magyarfalvi, 2008) involving slight modifications.

Recently, N-benzyl-3-nitroaniline was reported (Stilinović & Portada, 2011). The difference between the title compound and the previously reported one is only in methyl substituent on the N-benzyl moiety, since it was of interest to study the influence of the benzyl moiety substituents on the molecular conformation, and consequently the hydrogen bonding formation.

The addition of methyl substituent on the benzyl moiety in the title compound did not cause any significant conformational difference. The molecule retained a bent conformation with the torsion angle about the central C—N bond of 73.9 (2)° being very similar to analogous one in the recently reported compound (Stilinović & Portada, 2011). Furthermore, the N-methyl-3-nitroaniline system in the title compound is nearly ideally planar (r.m.s. deviation of the atoms C1–C7/N1/N2/O1/O2 from their mean plane is 0.0185 Å, with oxygen atom O2 being the one that deviates most from that plane, 0.031 (2) Å). The p-tolyl substituent is tilted at an angle of 89.79 (4)° to the rest of the molecule.

Two neighbouring molecules are connected through the set of N—H···O and C—H···O hydrogen bonds in the head to tail manner forming R²₂(8) motifs (Etter, 1990; Bernstein et al., 1995) that generate one-dimensional chains running in the [101] direction. The same hydrogen bonding pattern is also found in N-benzyl-3-nitroaniline (Stilinović & Portada, 2011) what leads to the conclusion that the methyl substituent in p-position to the central C—N bond do not influence neither hydrogen bonding geometry nor general hydrogen bonding framework formation.

Experimental

The title compound was prepared using a slightly modified procedure (Magyarfalvi, 2008) and isolated in a form of yellow crystalline product. Used: 3-nitroaniline (1.10 g; 7.96 mmol), p-tolualdehyde (1.74 ml; 1.77 g; 14.7 mmol), sodium tetrahydridoborate (0.50 g; 13.2 mmol). Yield: 1.12 g (58%). Upon re-crystallization in ethanol, yellow block-like crystalls suitable for the X-ray experiment were obtained in 3–4 days.