2-Bromo-4-methyl­benzonitrile

Shahid, M.; Munawar, M.A.; Nadeem, S.; Nasir, W.; Salim, M.

doi:10.1107/S1600536809048983

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3166

doi:10.1107/S1600536809048983

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2-Bromo-4-methylbenzonitrile

Muhammad Shahid,^a Munawar Ali Munawar,^a ^* Sohail Nadeem,^a Waqar Nasir ^a and Muhammad Salim ^a

^aInstitute of Chemistry, University of the Punjab, New Campus, Lahore, Pakistan
^*Correspondence e-mail: munawaralimunawar@yahoo.com

(Received 16 November 2009; accepted 17 November 2009; online 21 November 2009)

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 ). 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 ); Simon et al. (1989 ).

Experimental

Crystal data

C₈H₆BrN
M_r = 196.05
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.033
wR(F²) = 0.084
S = 1.01
1921 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.49 e Å⁻³

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

For the synthesis, see: Johnson & Sandborn (1941). 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); Simon et al. (1989).

Experimental top

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.

Computing details top

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

Figures top

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

2-bromo-4-methylbenzonitrile top

Crystal data top

C₈H₆BrN	Z = 2
M_r = 196.05	F(000) = 192
Triclinic, P1	D_x = 1.665 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5168 (11) Å	Cell parameters from 3073 reflections
b = 7.8383 (11) Å	θ = 2.2–21.2°
c = 7.9428 (11) Å	µ = 5.17 mm⁻¹
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 top

Bruker Kappa APEXII CCD diffractometer	1921 independent reflections
Radiation source: fine-focus sealed tube	1244 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→9
T_min = 0.226, T_max = 0.440	k = −10→10
8084 measured reflections	l = −10→10

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0326P)² + 0.2649P] where P = (F_o² + 2F_c²)/3
1921 reflections	(Δ/σ)_max < 0.001
92 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₈H₆BrN	γ = 87.567 (8)°
M_r = 196.05	V = 391.14 (10) Å³
Triclinic, P1	Z = 2
a = 7.5168 (11) Å	Mo Kα radiation
b = 7.8383 (11) Å	µ = 5.17 mm⁻¹
c = 7.9428 (11) Å	T = 296 K
α = 69.243 (7)°	0.41 × 0.28 × 0.19 mm
β = 64.375 (8)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1921 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1244 reflections with I > 2σ(I)
T_min = 0.226, T_max = 0.440	R_int = 0.025
8084 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.084	H-atom parameters constrained
S = 1.01	Δρ_max = 0.44 e Å⁻³
1921 reflections	Δρ_min = −0.49 e Å⁻³
92 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Br1	0.32613 (7)	0.89370 (4)	0.35907 (6)	0.07874 (19)
C1	0.2019 (4)	0.3498 (4)	0.7427 (4)	0.0525 (7)
C2	0.2395 (4)	0.5395 (4)	0.6606 (4)	0.0512 (7)
H2	0.2419	0.6033	0.7387	0.061*
C3	0.2732 (4)	0.6352 (4)	0.4660 (4)	0.0457 (6)
C4	0.2711 (4)	0.5439 (4)	0.3461 (4)	0.0445 (6)
C5	0.2349 (5)	0.3537 (4)	0.4270 (5)	0.0532 (7)
H5	0.2337	0.2899	0.3485	0.064*
C6	0.2008 (5)	0.2588 (4)	0.6222 (5)	0.0582 (8)
H6	0.1765	0.1310	0.6747	0.070*
C7	0.1639 (6)	0.2446 (5)	0.9569 (5)	0.0764 (10)
H7A	0.2191	0.3191	1.0006	0.115*
H7B	0.2253	0.1339	0.9654	0.115*
H7C	0.0231	0.2136	1.0415	0.115*
C8	0.3088 (5)	0.6413 (4)	0.1400 (5)	0.0540 (7)
N1	0.3389 (5)	0.7126 (4)	−0.0230 (5)	0.0771 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1226 (4)	0.0413 (2)	0.0893 (3)	0.01752 (18)	−0.0609 (3)	−0.02676 (18)
C1	0.0514 (18)	0.0578 (18)	0.0451 (17)	0.0061 (14)	−0.0231 (14)	−0.0136 (14)
C2	0.0571 (18)	0.0587 (18)	0.0515 (18)	0.0159 (14)	−0.0288 (15)	−0.0308 (15)
C3	0.0525 (17)	0.0403 (14)	0.0491 (17)	0.0096 (12)	−0.0251 (14)	−0.0193 (13)
C4	0.0449 (16)	0.0480 (16)	0.0410 (16)	0.0047 (12)	−0.0188 (13)	−0.0174 (13)
C5	0.0641 (19)	0.0478 (16)	0.0525 (18)	0.0029 (14)	−0.0249 (15)	−0.0249 (14)
C6	0.069 (2)	0.0437 (16)	0.056 (2)	0.0005 (14)	−0.0258 (16)	−0.0151 (15)
C7	0.086 (3)	0.085 (3)	0.050 (2)	0.007 (2)	−0.0321 (19)	−0.0132 (18)
C8	0.0586 (19)	0.0560 (18)	0.0478 (19)	−0.0003 (14)	−0.0225 (15)	−0.0205 (15)
N1	0.098 (2)	0.077 (2)	0.0512 (18)	−0.0056 (17)	−0.0332 (17)	−0.0171 (16)

Geometric parameters (Å, º) top

Br1—C3	1.882 (3)	C4—C8	1.440 (4)
C1—C2	1.380 (4)	C5—C6	1.371 (4)
C1—C6	1.384 (4)	C5—H5	0.9300
C1—C7	1.503 (4)	C6—H6	0.9300
C2—C3	1.368 (4)	C7—H7A	0.9600
C2—H2	0.9300	C7—H7B	0.9600
C3—C4	1.384 (4)	C7—H7C	0.9600
C4—C5	1.383 (4)	C8—N1	1.133 (4)

C2—C1—C6	118.2 (3)	C6—C5—H5	119.9
C2—C1—C7	121.0 (3)	C4—C5—H5	119.9
C6—C1—C7	120.8 (3)	C5—C6—C1	121.2 (3)
C3—C2—C1	121.0 (3)	C5—C6—H6	119.4
C3—C2—H2	119.5	C1—C6—H6	119.4
C1—C2—H2	119.5	C1—C7—H7A	109.5
C2—C3—C4	120.8 (3)	C1—C7—H7B	109.5
C2—C3—Br1	119.6 (2)	H7A—C7—H7B	109.5
C4—C3—Br1	119.6 (2)	C1—C7—H7C	109.5
C5—C4—C3	118.6 (3)	H7A—C7—H7C	109.5
C5—C4—C8	119.6 (3)	H7B—C7—H7C	109.5
C3—C4—C8	121.8 (3)	N1—C8—C4	177.7 (3)
C6—C5—C4	120.3 (3)

Experimental details

Crystal data
Chemical formula	C₈H₆BrN
M_r	196.05
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.5168 (11), 7.8383 (11), 7.9428 (11)
α, β, γ (°)	69.243 (7), 64.375 (8), 87.567 (8)
V (Å³)	391.14 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.17
Crystal size (mm)	0.41 × 0.28 × 0.19

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.226, 0.440
No. of measured, independent and observed [I > 2σ(I)] reflections	8084, 1921, 1244
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.084, 1.01
No. of reflections	1921
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.49

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Acknowledgements

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.

References

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