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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3166.
Published online 2009 November 21. doi:  10.1107/S1600536809048983
PMCID: PMC2972014

2-Bromo-4-methyl­benzonitrile

Abstract

The title mol­ecule, C8H6BrN, is almost planar (r.m.s. deviation for the non-H atoms = 0.008 Å). In the crystal, weak π–π stacking inter­actions [centroid–centroid separations = 3.782 (2) and 3.919 (2) Å] generate [100] columns of mol­ecules.

Related literature

For the synthesis, see: Johnson & Sandborn (1941 [triangle]). 2-Bromo-4-methyl­benzonitrile derivatives are used as inter­mediates in the synthesis of phthalocyanine dyes. For applications of phthalocyanine dyes in photo redox reactions and photodynamic cancer therapy, see: Simon & Sirlin (1989 [triangle]); Simon et al. (1989 [triangle]).

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Object name is e-65-o3166-scheme1.jpg

Experimental

Crystal data

  • C8H6BrN
  • M r = 196.05
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3166-efi1.jpg
  • a = 7.5168 (11) Å
  • b = 7.8383 (11) Å
  • c = 7.9428 (11) Å
  • α = 69.243 (7)°
  • β = 64.375 (8)°
  • γ = 87.567 (8)°
  • V = 391.14 (10) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 5.17 mm−1
  • T = 296 K
  • 0.41 × 0.28 × 0.19 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2007 [triangle]) T min = 0.226, T max = 0.440
  • 8084 measured reflections
  • 1921 independent reflections
  • 1244 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.084
  • S = 1.01
  • 1921 reflections
  • 92 parameters
  • H-atom parameters constrained
  • Δρmax = 0.44 e Å−3
  • Δρmin = −0.49 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809048983/hb5232sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809048983/hb5232Isup2.hkl

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

Acknowledgments

Muhammad Shahid acknowledges the Higher Education Commission of Pakistan for providing funds, the Institute of Chemistry, University of the Punjab, for providing research facilities and the Education Department, Government of the Punjab, for their co-operation.

supplementary crystallographic information

Comment

Synthesis of 2-bromo-4-methylbenzonitrile derivatives are important compounds due to their use as intermediates in the synthesis of phthalocyanine dyes. The substituted phthalocyanine dyes have been used for photo redox reactions (Simon & Sirlin, 1989) and photodynamic cancer therapy (Simon et al.. 1989).

The title compound(I) is almost planar. The cyano plane (C4/C8/N1) is oriented at a dihedral angle of 79.7 (3)° with respect to aromatic ring (C1/C2/C3/C4/C5/C6). The dihedral angle between the plane containing the methyl carbon (C1/C2/C6/C7) and aromatic ring plane is 0.22 (0.18)°. No significant intermolecular or intramolecular hydrogen bonding interaction has been observed in the molecule.

Experimental

3-Bromo-4-amino toluene (10 g, 54 mmol) (Johnson & Sandborn, 1941) was dissolved in HCl (30 ml, 17%). The mixture was cooled to 273 K in an ice-salt mixture. Over 5 min, an aqueous solution (9 ml) of NaNO2 (4.3 g) was added to the above mixture. The temperature was maintained at 273-278 K. A mixture of aqueous solution (6%) of Cu(I)cyanide and KCN (40%) was heated to 333 K and added to the above cold neutralized diazonium salt solution. After work up of reaction, colourless blocks of (I) were obtained by the slow evaporation of water.

Refinement

The H atoms were geometrically placed (C—H = 0.93–0.96Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of (I) with 50% displacement ellipsoids.
Fig. 2.
Unit cell packing diagram.

Crystal data

C8H6BrNZ = 2
Mr = 196.05F(000) = 192
Triclinic, P1Dx = 1.665 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.5168 (11) ÅCell parameters from 3073 reflections
b = 7.8383 (11) Åθ = 2.2–21.2°
c = 7.9428 (11) ŵ = 5.17 mm1
α = 69.243 (7)°T = 296 K
β = 64.375 (8)°Block, colourless
γ = 87.567 (8)°0.41 × 0.28 × 0.19 mm
V = 391.14 (10) Å3

Data collection

Bruker Kappa APEXII CCD diffractometer1921 independent reflections
Radiation source: fine-focus sealed tube1244 reflections with I > 2σ(I)
graphiteRint = 0.025
[var phi] and ω scansθmax = 28.3°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2007)h = −9→9
Tmin = 0.226, Tmax = 0.440k = −10→10
8084 measured reflectionsl = −10→10

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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.0326P)2 + 0.2649P] where P = (Fo2 + 2Fc2)/3
1921 reflections(Δ/σ)max < 0.001
92 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = −0.49 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Br10.32613 (7)0.89370 (4)0.35907 (6)0.07874 (19)
C10.2019 (4)0.3498 (4)0.7427 (4)0.0525 (7)
C20.2395 (4)0.5395 (4)0.6606 (4)0.0512 (7)
H20.24190.60330.73870.061*
C30.2732 (4)0.6352 (4)0.4660 (4)0.0457 (6)
C40.2711 (4)0.5439 (4)0.3461 (4)0.0445 (6)
C50.2349 (5)0.3537 (4)0.4270 (5)0.0532 (7)
H50.23370.28990.34850.064*
C60.2008 (5)0.2588 (4)0.6222 (5)0.0582 (8)
H60.17650.13100.67470.070*
C70.1639 (6)0.2446 (5)0.9569 (5)0.0764 (10)
H7A0.21910.31911.00060.115*
H7B0.22530.13390.96540.115*
H7C0.02310.21361.04150.115*
C80.3088 (5)0.6413 (4)0.1400 (5)0.0540 (7)
N10.3389 (5)0.7126 (4)−0.0230 (5)0.0771 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.1226 (4)0.0413 (2)0.0893 (3)0.01752 (18)−0.0609 (3)−0.02676 (18)
C10.0514 (18)0.0578 (18)0.0451 (17)0.0061 (14)−0.0231 (14)−0.0136 (14)
C20.0571 (18)0.0587 (18)0.0515 (18)0.0159 (14)−0.0288 (15)−0.0308 (15)
C30.0525 (17)0.0403 (14)0.0491 (17)0.0096 (12)−0.0251 (14)−0.0193 (13)
C40.0449 (16)0.0480 (16)0.0410 (16)0.0047 (12)−0.0188 (13)−0.0174 (13)
C50.0641 (19)0.0478 (16)0.0525 (18)0.0029 (14)−0.0249 (15)−0.0249 (14)
C60.069 (2)0.0437 (16)0.056 (2)0.0005 (14)−0.0258 (16)−0.0151 (15)
C70.086 (3)0.085 (3)0.050 (2)0.007 (2)−0.0321 (19)−0.0132 (18)
C80.0586 (19)0.0560 (18)0.0478 (19)−0.0003 (14)−0.0225 (15)−0.0205 (15)
N10.098 (2)0.077 (2)0.0512 (18)−0.0056 (17)−0.0332 (17)−0.0171 (16)

Geometric parameters (Å, °)

Br1—C31.882 (3)C4—C81.440 (4)
C1—C21.380 (4)C5—C61.371 (4)
C1—C61.384 (4)C5—H50.9300
C1—C71.503 (4)C6—H60.9300
C2—C31.368 (4)C7—H7A0.9600
C2—H20.9300C7—H7B0.9600
C3—C41.384 (4)C7—H7C0.9600
C4—C51.383 (4)C8—N11.133 (4)
C2—C1—C6118.2 (3)C6—C5—H5119.9
C2—C1—C7121.0 (3)C4—C5—H5119.9
C6—C1—C7120.8 (3)C5—C6—C1121.2 (3)
C3—C2—C1121.0 (3)C5—C6—H6119.4
C3—C2—H2119.5C1—C6—H6119.4
C1—C2—H2119.5C1—C7—H7A109.5
C2—C3—C4120.8 (3)C1—C7—H7B109.5
C2—C3—Br1119.6 (2)H7A—C7—H7B109.5
C4—C3—Br1119.6 (2)C1—C7—H7C109.5
C5—C4—C3118.6 (3)H7A—C7—H7C109.5
C5—C4—C8119.6 (3)H7B—C7—H7C109.5
C3—C4—C8121.8 (3)N1—C8—C4177.7 (3)
C6—C5—C4120.3 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5232).

References

  • Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
  • Johnson, J. R. & Sandborn, L. T. (1941). Org. Synth. Coll. 1, 111–116.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Simon, J., Bassoul, P. & Norvez, S. (1989). New. J. Chem 13, 13–31.
  • Simon, J. & Sirlin, C. (1989). Pure Appl. Chem. 61, 1625–1629.
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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