2-Methyl-3-nitro­benzyl cyanide

Chen, Y.-S.; Zhang, J.-H.

doi:10.1107/S1600536809008484

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o767

doi:10.1107/S1600536809008484

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2-Methyl-3-nitrobenzyl cyanide

You-Sheng Chen ^a ^* and Jian-Hong Zhang ^b

^aDepartment of Pharmacy, GuangDong Vocational and Technical College of Chemical Engineering Pharmaceutics, Guangzhou 510520, People's Republic of China, and ^bDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: njjhs@163.com

(Received 29 November 2008; accepted 8 March 2009; online 14 March 2009)

The title compound, C₉H₈N₂O, was prepared from o-xylene by nitration, oxidation, hydrolysis, reduction, chlorination and cyanation. There are two molecules in the asymmetric unit with a dihedral angle of 20.15 (7)° between their aromatic rings.

Related literature

For related literature, see: Wang et al. (1999 ).

Experimental

Crystal data

C₉H₈N₂O₂
M_r = 176.18
Monoclinic, P 2₁ /c
a = 17.216 (3) Å
b = 7.1950 (14) Å
c = 15.746 (3) Å
β = 117.10 (3)°
V = 1736.3 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.40 × 0.30 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.962, T_max = 0.981
3258 measured reflections
3129 independent reflections
2033 reflections with I > 2σ(I)
R_int = 0.029
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.073
wR(F²) = 0.197
S = 1.02
3129 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.29 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809008484/bq2111sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008484/bq2111Isup2.hkl

checkCIF report

Comment top

2-Methyl-3-nitrobenzyl cyanide is important chemical material of effective medicines used for Parkinson's disease, which can be useful not only for the treatment of PD, but also for the treatment of RLS. We report here the crystal structure of the title compound, (I), which is of interest to us in the field.

The molecular structure of (I) is shown in Fig.1, where the dash line indicates C—H···O hydrogen bonds (Table 2). The dihedral angle between the two aromatic rings of the molecules in the asymmetric unit is 20.15 (7)°.

Related literature top

For related literature, see: Wang et al. (1999).

Experimental top

The title compound, (I) was synthesized according to a literature reported before (Wang, 1999). The crystals were obtained by dissolving (I) (0.35 g, 2.0 mmol) into 25 ml of methanol and evaporating the solvent slowly at room temperature for about 4 d.

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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the molecular structure of (I), which is a asymmetric unit with two molecules, with the atom-labeling scheme. Displacement ellipsoids at the 30% probability level. Dash lines indicate C—H···O hydrogen bonds.

2-Methyl-3-nitrobenzyl cyanide top

Crystal data top

C₉H₈N₂O₂	F(000) = 736
M_r = 176.18	D_x = 1.348 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 17.216 (3) Å	θ = 10–13°
b = 7.1950 (14) Å	µ = 0.10 mm⁻¹
c = 15.746 (3) Å	T = 298 K
β = 117.10 (3)°	Block, yellow
V = 1736.3 (7) Å³	0.40 × 0.30 × 0.20 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	2033 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Graphite monochromator	θ_max = 25.2°, θ_min = 1.3°
ω/2θ scans	h = −20→18
Absorption correction: ψ scan (North et al., 1968)	k = 0→8
T_min = 0.962, T_max = 0.981	l = 0→18
3258 measured reflections	3 standard reflections every 200 reflections
3129 independent reflections	intensity decay: none

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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.197	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.06P)² + 2.6P] where P = (F_o² + 2F_c²)/3
3129 reflections	(Δ/σ)_max < 0.001
235 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₉H₈N₂O₂	V = 1736.3 (7) Å³
M_r = 176.18	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.216 (3) Å	µ = 0.10 mm⁻¹
b = 7.1950 (14) Å	T = 298 K
c = 15.746 (3) Å	0.40 × 0.30 × 0.20 mm
β = 117.10 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2033 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.029
T_min = 0.962, T_max = 0.981	3 standard reflections every 200 reflections
3258 measured reflections	intensity decay: none
3129 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.073	0 restraints
wR(F²) = 0.197	H-atom parameters constrained
S = 1.02	Δρ_max = 0.29 e Å⁻³
3129 reflections	Δρ_min = −0.27 e Å⁻³
235 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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	0.4276 (3)	0.7334 (6)	0.1977 (2)	0.1103 (13)
O2	0.3421 (2)	0.9322 (6)	0.0964 (3)	0.1045 (12)
N1	0.7122 (2)	0.5898 (7)	−0.0502 (3)	0.0945 (14)
N2	0.4027 (3)	0.8202 (6)	0.1242 (3)	0.0745 (10)
C1	0.6910 (2)	0.6447 (6)	0.0045 (3)	0.0697 (11)
C2	0.6654 (2)	0.7139 (6)	0.0738 (3)	0.0612 (10)
H2A	0.6923	0.8344	0.0959	0.073*
H2B	0.6878	0.6306	0.1282	0.073*
C3	0.5958 (3)	0.7856 (7)	0.2075 (2)	0.0795 (13)
H3A	0.6548	0.7639	0.2189	0.119*
H3B	0.5801	0.6965	0.2425	0.119*
H3C	0.5910	0.9088	0.2281	0.119*
C4	0.5348 (2)	0.7660 (5)	0.1016 (2)	0.0516 (9)
C5	0.4440 (2)	0.7870 (5)	0.0633 (2)	0.0497 (8)
C6	0.3884 (2)	0.7784 (5)	−0.0346 (2)	0.0552 (9)
H6A	0.3287	0.7966	−0.0579	0.066*
C7	0.4230 (2)	0.7427 (5)	−0.0959 (2)	0.0576 (9)
H7A	0.3867	0.7327	−0.1611	0.069*
C8	0.5115 (2)	0.7220 (5)	−0.0609 (2)	0.0511 (8)
H8A	0.5348	0.7000	−0.1029	0.061*
C9	0.5673 (2)	0.7334 (5)	0.0369 (2)	0.0517 (8)
O3	0.0637 (2)	0.2551 (6)	0.2586 (2)	0.1082 (13)
O4	0.1521 (2)	0.0640 (5)	0.2452 (2)	0.1002 (12)
N3	−0.2116 (2)	0.4233 (6)	−0.2708 (3)	0.0882 (12)
N4	0.0918 (2)	0.1720 (6)	0.2117 (2)	0.0720 (10)
C10	−0.1920 (2)	0.3586 (6)	−0.1986 (3)	0.0605 (10)
C11	−0.1684 (2)	0.2786 (6)	−0.1044 (2)	0.0602 (10)
H11A	−0.1940	0.1558	−0.1126	0.072*
H11B	−0.1932	0.3550	−0.0721	0.072*
C12	−0.1011 (3)	0.1927 (6)	0.0956 (3)	0.0706 (11)
H12A	−0.0745	0.1150	0.1511	0.106*
H12B	−0.1529	0.1338	0.0487	0.106*
H12C	−0.1160	0.3105	0.1129	0.106*
C13	−0.0386 (2)	0.2224 (5)	0.0551 (2)	0.0495 (8)
C14	0.0515 (2)	0.2114 (5)	0.1080 (2)	0.0512 (9)
C15	0.1095 (2)	0.2325 (5)	0.0709 (2)	0.0516 (8)
H15A	0.1693	0.2203	0.1094	0.062*
C16	0.0764 (2)	0.2721 (5)	−0.0249 (2)	0.0504 (8)
H16A	0.1139	0.2890	−0.0520	0.060*
C17	−0.0121 (2)	0.2867 (5)	−0.0803 (2)	0.0502 (8)
H17A	−0.0339	0.3126	−0.1450	0.060*
C18	−0.0704 (2)	0.2634 (5)	−0.0415 (2)	0.0458 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.128 (3)	0.158 (4)	0.0600 (19)	−0.017 (3)	0.055 (2)	−0.003 (2)
O2	0.086 (2)	0.132 (3)	0.116 (3)	0.003 (2)	0.063 (2)	−0.023 (2)
N1	0.055 (2)	0.133 (4)	0.092 (3)	0.008 (2)	0.030 (2)	−0.020 (3)
N2	0.071 (2)	0.097 (3)	0.060 (2)	−0.022 (2)	0.0345 (19)	−0.020 (2)
C1	0.0400 (19)	0.083 (3)	0.071 (3)	−0.003 (2)	0.0123 (19)	−0.007 (2)
C2	0.0457 (19)	0.075 (3)	0.053 (2)	−0.0042 (18)	0.0141 (17)	−0.0080 (19)
C3	0.075 (3)	0.109 (4)	0.0365 (19)	−0.012 (3)	0.0092 (18)	−0.013 (2)
C4	0.058 (2)	0.054 (2)	0.0315 (16)	−0.0093 (17)	0.0113 (15)	−0.0027 (15)
C5	0.058 (2)	0.0488 (19)	0.0431 (18)	−0.0086 (16)	0.0241 (16)	−0.0080 (16)
C6	0.0438 (18)	0.064 (2)	0.0459 (19)	−0.0013 (17)	0.0100 (15)	0.0042 (17)
C7	0.0483 (19)	0.072 (3)	0.0361 (17)	0.0021 (18)	0.0046 (15)	0.0037 (17)
C8	0.0519 (19)	0.063 (2)	0.0360 (17)	−0.0003 (17)	0.0175 (15)	−0.0011 (16)
C9	0.0432 (18)	0.054 (2)	0.0405 (17)	−0.0022 (16)	0.0039 (14)	−0.0031 (16)
O3	0.122 (3)	0.158 (4)	0.0441 (16)	−0.009 (3)	0.0369 (18)	−0.017 (2)
O4	0.093 (2)	0.117 (3)	0.0479 (17)	0.011 (2)	−0.0052 (16)	0.0230 (18)
N3	0.059 (2)	0.116 (3)	0.056 (2)	0.012 (2)	−0.0029 (17)	0.012 (2)
N4	0.080 (2)	0.088 (3)	0.0327 (16)	−0.010 (2)	0.0124 (17)	−0.0016 (18)
C10	0.0376 (18)	0.074 (3)	0.051 (2)	0.0045 (18)	0.0044 (16)	−0.001 (2)
C11	0.0456 (19)	0.072 (3)	0.052 (2)	0.0026 (18)	0.0125 (16)	−0.0015 (19)
C12	0.072 (3)	0.091 (3)	0.060 (2)	−0.009 (2)	0.041 (2)	0.001 (2)
C13	0.056 (2)	0.0479 (19)	0.0421 (18)	−0.0011 (16)	0.0200 (16)	−0.0057 (15)
C14	0.057 (2)	0.062 (2)	0.0262 (15)	−0.0049 (17)	0.0112 (14)	0.0005 (15)
C15	0.0441 (18)	0.056 (2)	0.0408 (17)	−0.0026 (16)	0.0069 (15)	−0.0022 (16)
C16	0.0410 (17)	0.067 (2)	0.0411 (18)	−0.0052 (16)	0.0167 (14)	−0.0049 (17)
C17	0.0472 (18)	0.063 (2)	0.0314 (16)	−0.0031 (16)	0.0099 (14)	0.0006 (15)
C18	0.0391 (16)	0.055 (2)	0.0357 (16)	−0.0007 (15)	0.0103 (14)	−0.0028 (15)

Geometric parameters (Å, º) top

O1—N2	1.209 (5)	O3—N4	1.209 (5)
O2—N2	1.231 (5)	O4—N4	1.209 (5)
N1—C1	1.148 (5)	N3—C10	1.129 (5)
N2—C5	1.451 (5)	N4—C14	1.483 (4)
C1—C2	1.440 (6)	C10—C11	1.465 (5)
C2—C9	1.522 (5)	C11—C18	1.521 (4)
C2—H2A	0.9700	C11—H11A	0.9700
C2—H2B	0.9700	C11—H11B	0.9700
C3—C4	1.519 (5)	C12—C13	1.492 (5)
C3—H3A	0.9600	C12—H12A	0.9600
C3—H3B	0.9600	C12—H12B	0.9600
C3—H3C	0.9600	C12—H12C	0.9600
C4—C9	1.388 (5)	C13—C14	1.389 (5)
C4—C5	1.404 (5)	C13—C18	1.394 (4)
C5—C6	1.397 (5)	C14—C15	1.375 (5)
C6—C7	1.370 (5)	C15—C16	1.378 (4)
C6—H6A	0.9300	C15—H15A	0.9300
C7—C8	1.371 (5)	C16—C17	1.372 (4)
C7—H7A	0.9300	C16—H16A	0.9300
C8—C9	1.396 (4)	C17—C18	1.402 (4)
C8—H8A	0.9300	C17—H17A	0.9300

O1—N2—O2	123.5 (4)	O4—N4—O3	123.7 (4)
O1—N2—C5	118.8 (4)	O4—N4—C14	118.8 (4)
O2—N2—C5	117.7 (4)	O3—N4—C14	117.5 (4)
N1—C1—C2	179.4 (4)	N3—C10—C11	178.2 (4)
C1—C2—C9	114.4 (3)	C10—C11—C18	113.6 (3)
C1—C2—H2A	108.7	C10—C11—H11A	108.8
C9—C2—H2A	108.7	C18—C11—H11A	108.8
C1—C2—H2B	108.7	C10—C11—H11B	108.8
C9—C2—H2B	108.7	C18—C11—H11B	108.8
H2A—C2—H2B	107.6	H11A—C11—H11B	107.7
C4—C3—H3A	109.5	C13—C12—H12A	109.5
C4—C3—H3B	109.5	C13—C12—H12B	109.5
H3A—C3—H3B	109.5	H12A—C12—H12B	109.5
C4—C3—H3C	109.5	C13—C12—H12C	109.5
H3A—C3—H3C	109.5	H12A—C12—H12C	109.5
H3B—C3—H3C	109.5	H12B—C12—H12C	109.5
C9—C4—C5	116.4 (3)	C14—C13—C18	116.1 (3)
C9—C4—C3	120.9 (3)	C14—C13—C12	124.2 (3)
C5—C4—C3	122.6 (3)	C18—C13—C12	119.7 (3)
C6—C5—C4	122.6 (3)	C15—C14—C13	124.6 (3)
C6—C5—N2	116.2 (3)	C15—C14—N4	115.0 (3)
C4—C5—N2	121.2 (3)	C13—C14—N4	120.3 (3)
C7—C6—C5	119.1 (3)	C14—C15—C16	117.9 (3)
C7—C6—H6A	120.5	C14—C15—H15A	121.0
C5—C6—H6A	120.5	C16—C15—H15A	121.0
C6—C7—C8	119.8 (3)	C17—C16—C15	119.8 (3)
C6—C7—H7A	120.1	C17—C16—H16A	120.1
C8—C7—H7A	120.1	C15—C16—H16A	120.1
C7—C8—C9	121.1 (3)	C16—C17—C18	121.5 (3)
C7—C8—H8A	119.4	C16—C17—H17A	119.3
C9—C8—H8A	119.4	C18—C17—H17A	119.3
C4—C9—C8	121.0 (3)	C13—C18—C17	119.9 (3)
C4—C9—C2	118.9 (3)	C13—C18—C11	119.5 (3)
C8—C9—C2	120.1 (3)	C17—C18—C11	120.6 (3)

N1—C1—C2—C9	173 (100)	N3—C10—C11—C18	−131 (15)
C9—C4—C5—C6	−0.8 (5)	C18—C13—C14—C15	−2.0 (5)
C3—C4—C5—C6	176.6 (4)	C12—C13—C14—C15	177.8 (4)
C9—C4—C5—N2	179.5 (3)	C18—C13—C14—N4	178.7 (3)
C3—C4—C5—N2	−3.0 (6)	C12—C13—C14—N4	−1.2 (5)
O1—N2—C5—C6	138.3 (4)	O4—N4—C14—C15	−41.7 (5)
O2—N2—C5—C6	−39.6 (5)	O3—N4—C14—C15	136.1 (4)
O1—N2—C5—C4	−42.1 (5)	O4—N4—C14—C13	137.5 (4)
O2—N2—C5—C4	140.0 (4)	O3—N4—C14—C13	−44.7 (5)
C4—C5—C6—C7	1.9 (6)	C13—C14—C15—C16	1.8 (6)
N2—C5—C6—C7	−178.4 (4)	N4—C14—C15—C16	−179.0 (3)
C5—C6—C7—C8	−2.1 (6)	C14—C15—C16—C17	−0.9 (5)
C6—C7—C8—C9	1.1 (6)	C15—C16—C17—C18	0.5 (5)
C5—C4—C9—C8	−0.2 (5)	C14—C13—C18—C17	1.4 (5)
C3—C4—C9—C8	−177.7 (4)	C12—C13—C18—C17	−178.2 (3)
C5—C4—C9—C2	178.6 (3)	C14—C13—C18—C11	−179.8 (3)
C3—C4—C9—C2	1.1 (5)	C12—C13—C18—C11	0.6 (5)
C7—C8—C9—C4	0.0 (6)	C16—C17—C18—C13	−0.7 (5)
C7—C8—C9—C2	−178.7 (3)	C16—C17—C18—C11	−179.5 (3)
C1—C2—C9—C4	168.4 (4)	C10—C11—C18—C13	168.2 (3)
C1—C2—C9—C8	−12.9 (5)	C10—C11—C18—C17	−13.0 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O1	0.96	2.40	2.852 (8)	108
C12—H12A···O3	0.96	2.42	2.864 (6)	108

Experimental details

Crystal data
Chemical formula	C₉H₈N₂O₂
M_r	176.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	17.216 (3), 7.1950 (14), 15.746 (3)
β (°)	117.10 (3)
V (Å³)	1736.3 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.962, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	3258, 3129, 2033
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.197, 1.02
No. of reflections	3129
No. of parameters	235
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −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
C3—H3B···O1	0.9600	2.4000	2.852 (8)	108.00
C12—H12A···O3	0.9600	2.4200	2.864 (6)	108.00

References

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o767

doi:10.1107/S1600536809008484

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