2-Methyl-3-nitro­benzonitrile

Han, G.; Han, L.; Lu, R.; Zhang, M.; Wang, H.

doi:10.1107/S1600536808039354

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2468

doi:10.1107/S1600536808039354

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2-Methyl-3-nitrobenzonitrile

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

^aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: wanghaibo@njut.edu.cn

(Received 14 November 2008; accepted 23 November 2008; online 29 November 2008)

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, P 2₁ /n
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[F² > 2σ(F²)] = 0.076
wR(F²) = 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

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
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+2, -y+1, -z+2; (iii) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines.

2-Methyl-3-nitrobenzonitrile top

Crystal data top

C₈H₆N₂O₂	F(000) = 672
M_r = 162.15	D_x = 1.369 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 14.025 (3) Å	θ = 9–12°
b = 7.3860 (15) Å	µ = 0.10 mm⁻¹
c = 15.515 (3) Å	T = 294 K
β = 101.80 (3)°	Block, colorless
V = 1573.2 (6) Å³	0.30 × 0.20 × 0.10 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	1481 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.069
Graphite monochromator	θ_max = 25.3°, θ_min = 1.8°
ω/2θ scans	h = 0→16
Absorption correction: ψ scan (North et al., 1968)	k = 0→8
T_min = 0.970, T_max = 0.990	l = −18→18
2974 measured reflections	3 standard reflections every 120 min
2852 independent reflections	intensity decay: 1%

Refinement top

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.170	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.04P)² + 1.75P] where P = (F_o² + 2F_c²)/3
2852 reflections	(Δ/σ)_max < 0.001
217 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₈H₆N₂O₂	V = 1573.2 (6) Å³
M_r = 162.15	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.025 (3) Å	µ = 0.10 mm⁻¹
b = 7.3860 (15) Å	T = 294 K
c = 15.515 (3) Å	0.30 × 0.20 × 0.10 mm
β = 101.80 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1481 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.069
T_min = 0.970, T_max = 0.990	3 standard reflections every 120 min
2974 measured reflections	intensity decay: 1%
2852 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.076	0 restraints
wR(F²) = 0.170	H-atom parameters constrained
S = 1.01	Δρ_max = 0.25 e Å⁻³
2852 reflections	Δρ_min = −0.27 e Å⁻³
217 parameters

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O1	0.8903 (3)	0.3923 (5)	0.9651 (2)	0.1022 (11)
O2	0.8075 (3)	0.2944 (5)	0.8476 (2)	0.1053 (12)
O3	−0.2355 (3)	−0.1305 (6)	0.2733 (2)	0.1165 (13)
O4	−0.2358 (2)	0.0205 (5)	0.3874 (2)	0.0933 (10)
N1	0.9792 (3)	−0.4285 (6)	0.7823 (3)	0.0911 (13)
N2	0.8813 (3)	0.2924 (5)	0.9055 (2)	0.0679 (9)
N3	0.1646 (3)	0.3683 (6)	0.4808 (3)	0.0913 (12)
N4	−0.1954 (3)	−0.0405 (6)	0.3328 (3)	0.0848 (12)
C1	0.8268 (3)	−0.0774 (7)	0.8368 (3)	0.0923 (16)
H1A	0.7835	0.0171	0.8470	0.139*
H1B	0.8181	−0.1816	0.8713	0.139*
H1C	0.8128	−0.1092	0.7755	0.139*
C2	0.9291 (3)	−0.0132 (5)	0.8624 (2)	0.0510 (9)
C3	0.9574 (2)	0.1578 (5)	0.8973 (2)	0.0485 (9)
C4	1.0540 (3)	0.2126 (6)	0.9250 (2)	0.0674 (11)
H4A	1.0702	0.3263	0.9494	0.081*
C5	1.1250 (3)	0.0870 (7)	0.9140 (3)	0.0735 (12)
H5A	1.1903	0.1195	0.9309	0.088*
C6	1.1036 (3)	−0.0738 (6)	0.8811 (3)	0.0687 (11)
H6A	1.1534	−0.1538	0.8760	0.082*
C7	1.0072 (3)	−0.1268 (5)	0.8534 (2)	0.0538 (9)
C8	0.9868 (3)	−0.3022 (6)	0.8160 (3)	0.0743 (13)
C9	−0.0871 (3)	0.2856 (5)	0.4071 (3)	0.0707 (11)
H9A	−0.0390	0.3709	0.4351	0.106*
H9B	−0.1311	0.2595	0.4455	0.106*
H9C	−0.1228	0.3360	0.3531	0.106*
C10	−0.0378 (3)	0.1138 (5)	0.3880 (2)	0.0472 (8)
C11	−0.0849 (3)	−0.0391 (6)	0.3503 (2)	0.0573 (10)
C12	−0.0389 (3)	−0.1889 (6)	0.3260 (2)	0.0669 (11)
H12A	−0.0752	−0.2850	0.2977	0.080*
C13	0.0618 (3)	−0.1963 (6)	0.3435 (3)	0.0733 (12)
H13A	0.0943	−0.2984	0.3295	0.088*
C14	0.1137 (3)	−0.0442 (5)	0.3834 (2)	0.0609 (10)
H14A	0.1814	−0.0446	0.3950	0.073*
C15	0.0650 (3)	0.1033 (5)	0.4049 (2)	0.0509 (9)
C16	0.1190 (3)	0.2561 (6)	0.4443 (3)	0.0646 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.115 (3)	0.095 (3)	0.102 (3)	0.006 (2)	0.033 (2)	−0.014 (2)
O2	0.098 (3)	0.108 (3)	0.108 (3)	0.018 (2)	0.016 (2)	−0.001 (2)
O3	0.099 (3)	0.144 (4)	0.106 (3)	−0.008 (3)	0.018 (2)	−0.010 (3)
O4	0.076 (2)	0.106 (3)	0.102 (2)	−0.0009 (19)	0.0258 (18)	−0.004 (2)
N1	0.115 (3)	0.071 (3)	0.087 (3)	0.004 (2)	0.020 (2)	−0.012 (2)
N2	0.079 (2)	0.064 (2)	0.065 (2)	0.014 (2)	0.0264 (19)	0.003 (2)
N3	0.089 (3)	0.085 (3)	0.101 (3)	−0.008 (2)	0.023 (2)	−0.017 (2)
N4	0.075 (3)	0.097 (3)	0.084 (3)	−0.011 (2)	0.020 (2)	0.005 (3)
C1	0.064 (3)	0.116 (4)	0.106 (4)	−0.020 (3)	0.037 (3)	−0.017 (3)
C2	0.056 (2)	0.053 (2)	0.052 (2)	−0.0032 (17)	0.0298 (17)	0.0022 (17)
C3	0.055 (2)	0.050 (2)	0.0460 (19)	0.0118 (17)	0.0226 (15)	−0.0005 (17)
C4	0.062 (2)	0.071 (3)	0.073 (3)	−0.007 (2)	0.0210 (19)	0.002 (2)
C5	0.051 (2)	0.091 (3)	0.083 (3)	−0.006 (2)	0.021 (2)	0.003 (3)
C6	0.068 (3)	0.076 (3)	0.074 (3)	0.016 (2)	0.041 (2)	0.008 (2)
C7	0.072 (2)	0.045 (2)	0.054 (2)	0.0078 (18)	0.0355 (18)	0.0067 (17)
C8	0.099 (4)	0.056 (3)	0.072 (3)	0.006 (3)	0.027 (2)	0.005 (2)
C9	0.070 (3)	0.067 (3)	0.081 (3)	0.009 (2)	0.031 (2)	−0.004 (2)
C10	0.059 (2)	0.0440 (19)	0.0454 (18)	0.0023 (17)	0.0260 (16)	0.0087 (16)
C11	0.053 (2)	0.069 (2)	0.053 (2)	−0.0123 (19)	0.0170 (16)	0.0077 (19)
C12	0.084 (3)	0.056 (2)	0.066 (2)	−0.021 (2)	0.029 (2)	−0.006 (2)
C13	0.091 (3)	0.064 (3)	0.075 (3)	0.000 (2)	0.041 (2)	−0.008 (2)
C14	0.058 (2)	0.065 (2)	0.064 (2)	0.0003 (19)	0.0224 (18)	−0.007 (2)
C15	0.055 (2)	0.054 (2)	0.048 (2)	−0.0040 (18)	0.0199 (16)	0.0038 (17)
C16	0.064 (3)	0.060 (3)	0.078 (3)	−0.004 (2)	0.034 (2)	−0.014 (2)

Geometric parameters (Å, º) top

O1—N2	1.169 (4)	C5—H5A	0.9300
O2—N2	1.224 (4)	C6—C7	1.388 (5)
O3—N4	1.182 (5)	C6—H6A	0.9300
O4—N4	1.200 (5)	C7—C8	1.425 (6)
N1—C8	1.063 (5)	C9—C10	1.504 (5)
N2—C3	1.483 (4)	C9—H9A	0.9600
N3—C16	1.125 (5)	C9—H9B	0.9600
N4—C11	1.518 (5)	C9—H9C	0.9600
C1—C2	1.485 (5)	C10—C11	1.376 (5)
C1—H1A	0.9600	C10—C15	1.414 (5)
C1—H1B	0.9600	C11—C12	1.372 (5)
C1—H1C	0.9600	C12—C13	1.384 (5)
C2—C3	1.399 (5)	C12—H12A	0.9300
C2—C7	1.410 (5)	C13—C14	1.410 (5)
C3—C4	1.396 (5)	C13—H13A	0.9300
C4—C5	1.396 (6)	C14—C15	1.363 (5)
C4—H4A	0.9300	C14—H14A	0.9300
C5—C6	1.304 (6)	C15—C16	1.426 (5)

O1—N2—O2	120.7 (4)	C6—C7—C8	119.0 (4)
O1—N2—C3	121.9 (4)	C2—C7—C8	119.0 (4)
O2—N2—C3	117.4 (4)	N1—C8—C7	171.6 (6)
O3—N4—O4	122.9 (5)	C10—C9—H9A	109.5
O3—N4—C11	116.7 (4)	C10—C9—H9B	109.5
O4—N4—C11	119.0 (4)	H9A—C9—H9B	109.5
C2—C1—H1A	109.5	C10—C9—H9C	109.5
C2—C1—H1B	109.5	H9A—C9—H9C	109.5
H1A—C1—H1B	109.5	H9B—C9—H9C	109.5
C2—C1—H1C	109.5	C11—C10—C15	114.6 (3)
H1A—C1—H1C	109.5	C11—C10—C9	125.2 (3)
H1B—C1—H1C	109.5	C15—C10—C9	120.2 (3)
C3—C2—C7	114.3 (3)	C12—C11—C10	124.5 (4)
C3—C2—C1	125.0 (4)	C12—C11—N4	117.8 (4)
C7—C2—C1	120.7 (4)	C10—C11—N4	117.7 (4)
C4—C3—C2	124.2 (3)	C11—C12—C13	119.7 (4)
C4—C3—N2	116.7 (3)	C11—C12—H12A	120.1
C2—C3—N2	119.1 (3)	C13—C12—H12A	120.1
C3—C4—C5	116.3 (4)	C12—C13—C14	118.0 (4)
C3—C4—H4A	121.9	C12—C13—H13A	121.0
C5—C4—H4A	121.9	C14—C13—H13A	121.0
C6—C5—C4	122.7 (4)	C15—C14—C13	120.3 (4)
C6—C5—H5A	118.7	C15—C14—H14A	119.9
C4—C5—H5A	118.7	C13—C14—H14A	119.9
C5—C6—C7	120.7 (4)	C14—C15—C10	122.8 (3)
C5—C6—H6A	119.7	C14—C15—C16	119.3 (3)
C7—C6—H6A	119.7	C10—C15—C16	117.9 (3)
C6—C7—C2	121.9 (4)	N3—C16—C15	174.6 (5)

Hydrogen-bond geometry (Å, º) top

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

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

Experimental details

Crystal data
Chemical formula	C₈H₆N₂O₂
M_r	162.15
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	14.025 (3), 7.3860 (15), 15.515 (3)
β (°)	101.80 (3)
V (Å³)	1573.2 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.970, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	2974, 2852, 1481
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.076, 0.170, 1.01
No. of reflections	2852
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.27

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O2	0.96	2.08	2.768 (6)	128.00
C1—H1C···O2ⁱ	0.96	2.38	3.229 (6)	147.00
C4—H4A···O1ⁱⁱ	0.93	2.47	3.390 (6)	171.00
C9—H9B···O4	0.96	2.35	2.831 (5)	110.00
C9—H9C···O3ⁱⁱⁱ	0.96	2.50	3.400 (4)	156.00

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Suzuki, H., Tomaru, J. & Murashima, T. (1994). J. Chem. Soc. Perkin Trans. 1, pp. 2413–2416. CrossRef Web of Science Google Scholar
Xinhua, P., Naoyuki, F. & Masayuki, M. (2003). Org. Biomol. Chem. 1, 2326–2335. Web of Science PubMed Google Scholar

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COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2468

doi:10.1107/S1600536808039354

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