2-Methyl-3-nitro­benzonitrile

Guo-zhi Han; Lu-na Han; Ran-zhe Lu; Min Zhang; Hai-bo Wang

doi:10.1107/S1600536808039354

. 2008 Nov 29;64(Pt 12):o2468. doi: 10.1107/S1600536808039354

2-Methyl-3-nitrobenzonitrile

Guo-zhi Han ^a, Lu-na Han ^a, Ran-zhe Lu ^a, Min Zhang ^a, Hai-bo Wang ^a,^*

PMCID: PMC2959969 PMID: 21581435

Abstract

The asymmetric unit of the title compound, C₈H₆N₂O₂, contains two independent molecules, the aromatic rings of which are oriented at a dihedral angle of 1.68 (3)°. Intramolecular C—H⋯O hydrogen bonds result in the formation of two non-planar six-membered rings, which adopt envelope and twisted conformations. In the crystal structure, intermolecular C—H⋯O hydrogen bonds link the molecules. There are π–π contacts between the benzene rings [centroid–centroid distances = 3.752 (3) and 3.874 (3) Å].

Related literature

For general background, see: Suzuki et al. (1994 ▶). For a related structure, see: Xinhua et al. (2003 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₈H₆N₂O₂
M _r = 162.15
Monoclinic,
a = 14.025 (3) Å
b = 7.3860 (15) Å
c = 15.515 (3) Å
β = 101.80 (3)°
V = 1573.2 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 294 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.970, T _max = 0.990
2974 measured reflections
2852 independent reflections
1481 reflections with I > 2σ(I)
R _int = 0.069
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.076
wR(F ²) = 0.170
S = 1.01
2852 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039354/hk2576sup1.cif

e-64-o2468-sup1.cif^{(16.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808039354/hk2576Isup2.hkl

e-64-o2468-Isup2.hkl^{(139.8KB, 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
C1—H1A⋯O2	0.96	2.08	2.768 (6)	128
C1—H1C⋯O2ⁱ	0.96	2.38	3.229 (6)	147
C4—H4A⋯O1ⁱⁱ	0.93	2.47	3.390 (6)	171
C9—H9B⋯O4	0.96	2.35	2.831 (5)	110
C9—H9C⋯O3ⁱⁱⁱ	0.96	2.50	3.400 (4)	156

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

supplementary crystallographic information

Comment

Benzonitrile is an important pharmaceutical intermediate, many of its derivatives have biological activity and be used as a variety of drugs. Benzonitrile was found to be almost inert toward the combined action of nitrogen dioxide and dioxygen at room temperature (Suzuki et al., 1994). We report herein the crystal structure of the title compound.

The asymmetric unit of the title compound, (Fig. 1), contains two crystallographically independent molecules, in which the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C2-C7) and B (C10-C15) are, of course, planar, and they are oriented at a dihedral angle of 1.68 (3)°. The intramolecular C-H···O hydrogen bonds result in the formation of two nonplanar six-membered rings C (O2/N2/C1-C3/H1A) and D (O4/N4/C9-C11/H9B). Ring C adopts envelope conformation with O2 atom displaced by 0.690 (3) Å from the plane of the other ring atoms, while ring D has twisted conformation.

In the crystal structure, intermolecular C-H···O hydrogen bonds (Table 1) link the molecules, in which they may be effective in the stabilization of the structure. The π-π contacts between the benzene rings Cg1···Cg1ⁱ and Cg1···Cg2ⁱⁱ [symmetry codes: (i) -x, 2 - y, -z, (ii) 1/2 - x, 1/2 + y, 1/2 - z, where Cg1 and Cg2 are centroids of the rings A (C2-C7) and B (C10-C15), respectively] may further stabilize the structure, with centroid-centroid distances of 3.752 (3) %A and 3.874 (3) %A, respectively.

Experimental

The title compound is synthesized according to the literature method (Xinhua et al., 2003). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.