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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o767.
Published online 2009 March 14. doi:  10.1107/S1600536809008484
PMCID: PMC2968898

2-Methyl-3-nitro­benzyl cyanide

Abstract

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 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o767-scheme1.jpg

Experimental

Crystal data

  • C9H8N2O2
  • M r = 176.18
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o767-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.073
  • wR(F 2) = 0.197
  • S = 1.02
  • 3129 reflections
  • 235 parameters
  • H-atom parameters constrained
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.27 e Å−3

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

Supplementary Material

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

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

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

supplementary crystallographic information

Comment

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)°.

Experimental

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.

Refinement

All H atoms bonded to the C atoms were placed geometrically at the distances of 0.93–0.97Å and included in the refinement in riding motion approximation with Uiso(H) = 1.2Ueq of the carrier atom. The O—H and N—H distances were constrained to 0.82Å and 0.86Å and these H atoms were refined as riding, with Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O).

Figures

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.

Crystal data

C9H8N2O2F(000) = 736
Mr = 176.18Dx = 1.348 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 17.216 (3) Åθ = 10–13°
b = 7.1950 (14) ŵ = 0.10 mm1
c = 15.746 (3) ÅT = 298 K
β = 117.10 (3)°Block, yellow
V = 1736.3 (7) Å30.40 × 0.30 × 0.20 mm
Z = 8

Data collection

Enraf–Nonius CAD-4 diffractometer2033 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.029
graphiteθmax = 25.2°, θmin = 1.3°
ω/2θ scansh = −20→18
Absorption correction: ψ scan (North et al., 1968)k = 0→8
Tmin = 0.962, Tmax = 0.981l = 0→18
3258 measured reflections3 standard reflections every 200 reflections
3129 independent reflections intensity decay: none

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.073Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.197H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.06P)2 + 2.6P] where P = (Fo2 + 2Fc2)/3
3129 reflections(Δ/σ)max < 0.001
235 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = −0.27 e Å3

Special details

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)

xyzUiso*/Ueq
O10.4276 (3)0.7334 (6)0.1977 (2)0.1103 (13)
O20.3421 (2)0.9322 (6)0.0964 (3)0.1045 (12)
N10.7122 (2)0.5898 (7)−0.0502 (3)0.0945 (14)
N20.4027 (3)0.8202 (6)0.1242 (3)0.0745 (10)
C10.6910 (2)0.6447 (6)0.0045 (3)0.0697 (11)
C20.6654 (2)0.7139 (6)0.0738 (3)0.0612 (10)
H2A0.69230.83440.09590.073*
H2B0.68780.63060.12820.073*
C30.5958 (3)0.7856 (7)0.2075 (2)0.0795 (13)
H3A0.65480.76390.21890.119*
H3B0.58010.69650.24250.119*
H3C0.59100.90880.22810.119*
C40.5348 (2)0.7660 (5)0.1016 (2)0.0516 (9)
C50.4440 (2)0.7870 (5)0.0633 (2)0.0497 (8)
C60.3884 (2)0.7784 (5)−0.0346 (2)0.0552 (9)
H6A0.32870.7966−0.05790.066*
C70.4230 (2)0.7427 (5)−0.0959 (2)0.0576 (9)
H7A0.38670.7327−0.16110.069*
C80.5115 (2)0.7220 (5)−0.0609 (2)0.0511 (8)
H8A0.53480.7000−0.10290.061*
C90.5673 (2)0.7334 (5)0.0369 (2)0.0517 (8)
O30.0637 (2)0.2551 (6)0.2586 (2)0.1082 (13)
O40.1521 (2)0.0640 (5)0.2452 (2)0.1002 (12)
N3−0.2116 (2)0.4233 (6)−0.2708 (3)0.0882 (12)
N40.0918 (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−0.19400.1558−0.11260.072*
H11B−0.19320.3550−0.07210.072*
C12−0.1011 (3)0.1927 (6)0.0956 (3)0.0706 (11)
H12A−0.07450.11500.15110.106*
H12B−0.15290.13380.04870.106*
H12C−0.11600.31050.11290.106*
C13−0.0386 (2)0.2224 (5)0.0551 (2)0.0495 (8)
C140.0515 (2)0.2114 (5)0.1080 (2)0.0512 (9)
C150.1095 (2)0.2325 (5)0.0709 (2)0.0516 (8)
H15A0.16930.22030.10940.062*
C160.0764 (2)0.2721 (5)−0.0249 (2)0.0504 (8)
H16A0.11390.2890−0.05200.060*
C17−0.0121 (2)0.2867 (5)−0.0803 (2)0.0502 (8)
H17A−0.03390.3126−0.14500.060*
C18−0.0704 (2)0.2634 (5)−0.0415 (2)0.0458 (8)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.128 (3)0.158 (4)0.0600 (19)−0.017 (3)0.055 (2)−0.003 (2)
O20.086 (2)0.132 (3)0.116 (3)0.003 (2)0.063 (2)−0.023 (2)
N10.055 (2)0.133 (4)0.092 (3)0.008 (2)0.030 (2)−0.020 (3)
N20.071 (2)0.097 (3)0.060 (2)−0.022 (2)0.0345 (19)−0.020 (2)
C10.0400 (19)0.083 (3)0.071 (3)−0.003 (2)0.0123 (19)−0.007 (2)
C20.0457 (19)0.075 (3)0.053 (2)−0.0042 (18)0.0141 (17)−0.0080 (19)
C30.075 (3)0.109 (4)0.0365 (19)−0.012 (3)0.0092 (18)−0.013 (2)
C40.058 (2)0.054 (2)0.0315 (16)−0.0093 (17)0.0113 (15)−0.0027 (15)
C50.058 (2)0.0488 (19)0.0431 (18)−0.0086 (16)0.0241 (16)−0.0080 (16)
C60.0438 (18)0.064 (2)0.0459 (19)−0.0013 (17)0.0100 (15)0.0042 (17)
C70.0483 (19)0.072 (3)0.0361 (17)0.0021 (18)0.0046 (15)0.0037 (17)
C80.0519 (19)0.063 (2)0.0360 (17)−0.0003 (17)0.0175 (15)−0.0011 (16)
C90.0432 (18)0.054 (2)0.0405 (17)−0.0022 (16)0.0039 (14)−0.0031 (16)
O30.122 (3)0.158 (4)0.0441 (16)−0.009 (3)0.0369 (18)−0.017 (2)
O40.093 (2)0.117 (3)0.0479 (17)0.011 (2)−0.0052 (16)0.0230 (18)
N30.059 (2)0.116 (3)0.056 (2)0.012 (2)−0.0029 (17)0.012 (2)
N40.080 (2)0.088 (3)0.0327 (16)−0.010 (2)0.0124 (17)−0.0016 (18)
C100.0376 (18)0.074 (3)0.051 (2)0.0045 (18)0.0044 (16)−0.001 (2)
C110.0456 (19)0.072 (3)0.052 (2)0.0026 (18)0.0125 (16)−0.0015 (19)
C120.072 (3)0.091 (3)0.060 (2)−0.009 (2)0.041 (2)0.001 (2)
C130.056 (2)0.0479 (19)0.0421 (18)−0.0011 (16)0.0200 (16)−0.0057 (15)
C140.057 (2)0.062 (2)0.0262 (15)−0.0049 (17)0.0112 (14)0.0005 (15)
C150.0441 (18)0.056 (2)0.0408 (17)−0.0026 (16)0.0069 (15)−0.0022 (16)
C160.0410 (17)0.067 (2)0.0411 (18)−0.0052 (16)0.0167 (14)−0.0049 (17)
C170.0472 (18)0.063 (2)0.0314 (16)−0.0031 (16)0.0099 (14)0.0006 (15)
C180.0391 (16)0.055 (2)0.0357 (16)−0.0007 (15)0.0103 (14)−0.0028 (15)

Geometric parameters (Å, °)

O1—N21.209 (5)O3—N41.209 (5)
O2—N21.231 (5)O4—N41.209 (5)
N1—C11.148 (5)N3—C101.129 (5)
N2—C51.451 (5)N4—C141.483 (4)
C1—C21.440 (6)C10—C111.465 (5)
C2—C91.522 (5)C11—C181.521 (4)
C2—H2A0.9700C11—H11A0.9700
C2—H2B0.9700C11—H11B0.9700
C3—C41.519 (5)C12—C131.492 (5)
C3—H3A0.9600C12—H12A0.9600
C3—H3B0.9600C12—H12B0.9600
C3—H3C0.9600C12—H12C0.9600
C4—C91.388 (5)C13—C141.389 (5)
C4—C51.404 (5)C13—C181.394 (4)
C5—C61.397 (5)C14—C151.375 (5)
C6—C71.370 (5)C15—C161.378 (4)
C6—H6A0.9300C15—H15A0.9300
C7—C81.371 (5)C16—C171.372 (4)
C7—H7A0.9300C16—H16A0.9300
C8—C91.396 (4)C17—C181.402 (4)
C8—H8A0.9300C17—H17A0.9300
O1—N2—O2123.5 (4)O4—N4—O3123.7 (4)
O1—N2—C5118.8 (4)O4—N4—C14118.8 (4)
O2—N2—C5117.7 (4)O3—N4—C14117.5 (4)
N1—C1—C2179.4 (4)N3—C10—C11178.2 (4)
C1—C2—C9114.4 (3)C10—C11—C18113.6 (3)
C1—C2—H2A108.7C10—C11—H11A108.8
C9—C2—H2A108.7C18—C11—H11A108.8
C1—C2—H2B108.7C10—C11—H11B108.8
C9—C2—H2B108.7C18—C11—H11B108.8
H2A—C2—H2B107.6H11A—C11—H11B107.7
C4—C3—H3A109.5C13—C12—H12A109.5
C4—C3—H3B109.5C13—C12—H12B109.5
H3A—C3—H3B109.5H12A—C12—H12B109.5
C4—C3—H3C109.5C13—C12—H12C109.5
H3A—C3—H3C109.5H12A—C12—H12C109.5
H3B—C3—H3C109.5H12B—C12—H12C109.5
C9—C4—C5116.4 (3)C14—C13—C18116.1 (3)
C9—C4—C3120.9 (3)C14—C13—C12124.2 (3)
C5—C4—C3122.6 (3)C18—C13—C12119.7 (3)
C6—C5—C4122.6 (3)C15—C14—C13124.6 (3)
C6—C5—N2116.2 (3)C15—C14—N4115.0 (3)
C4—C5—N2121.2 (3)C13—C14—N4120.3 (3)
C7—C6—C5119.1 (3)C14—C15—C16117.9 (3)
C7—C6—H6A120.5C14—C15—H15A121.0
C5—C6—H6A120.5C16—C15—H15A121.0
C6—C7—C8119.8 (3)C17—C16—C15119.8 (3)
C6—C7—H7A120.1C17—C16—H16A120.1
C8—C7—H7A120.1C15—C16—H16A120.1
C7—C8—C9121.1 (3)C16—C17—C18121.5 (3)
C7—C8—H8A119.4C16—C17—H17A119.3
C9—C8—H8A119.4C18—C17—H17A119.3
C4—C9—C8121.0 (3)C13—C18—C17119.9 (3)
C4—C9—C2118.9 (3)C13—C18—C11119.5 (3)
C8—C9—C2120.1 (3)C17—C18—C11120.6 (3)
N1—C1—C2—C9173 (100)N3—C10—C11—C18−131 (15)
C9—C4—C5—C6−0.8 (5)C18—C13—C14—C15−2.0 (5)
C3—C4—C5—C6176.6 (4)C12—C13—C14—C15177.8 (4)
C9—C4—C5—N2179.5 (3)C18—C13—C14—N4178.7 (3)
C3—C4—C5—N2−3.0 (6)C12—C13—C14—N4−1.2 (5)
O1—N2—C5—C6138.3 (4)O4—N4—C14—C15−41.7 (5)
O2—N2—C5—C6−39.6 (5)O3—N4—C14—C15136.1 (4)
O1—N2—C5—C4−42.1 (5)O4—N4—C14—C13137.5 (4)
O2—N2—C5—C4140.0 (4)O3—N4—C14—C13−44.7 (5)
C4—C5—C6—C71.9 (6)C13—C14—C15—C161.8 (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—C91.1 (6)C15—C16—C17—C180.5 (5)
C5—C4—C9—C8−0.2 (5)C14—C13—C18—C171.4 (5)
C3—C4—C9—C8−177.7 (4)C12—C13—C18—C17−178.2 (3)
C5—C4—C9—C2178.6 (3)C14—C13—C18—C11−179.8 (3)
C3—C4—C9—C21.1 (5)C12—C13—C18—C110.6 (5)
C7—C8—C9—C40.0 (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—C4168.4 (4)C10—C11—C18—C13168.2 (3)
C1—C2—C9—C8−12.9 (5)C10—C11—C18—C17−13.0 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C3—H3B···O10.962.402.852 (8)108
C12—H12A···O30.962.422.864 (6)108

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BQ2111).

References

  • Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, S. Q., Deng, X. Y. & Wang, S. J. (1999). Shenyang Yaoke Daxue Xuebao, 17, 103–104.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography