4-Bromo-1-nitro­benzene

Ali, Q.; Raza Shah, M.; Ng, S.W.

doi:10.1107/S1600536811003394

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o548

doi:10.1107/S1600536811003394

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4-Bromo-1-nitrobenzene

Qamar Ali,^a M. Raza Shah ^a and Seik Weng Ng ^b ^*

^aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 7527, Pakistan, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 22 January 2011; accepted 25 January 2011; online 2 February 2011)

The non-H atoms of the title molecule, C₆H₄BrNO₂, are essentially coplanar with an r.m.s. deviation of 0.040 Å. In the crystal, π–π stacking occurs between parallel benzene rings of adjacent molecules with centroid–centroid distances of 3.643 (3) and 3.741 (3) Å. Weak intermolecular C—H⋯O hydrogen bonding and short Br⋯O contacts [3.227 (4) 3.401 (4) Å] are also observed in the crystal structure. The crystal studied was a non-morohedral twin with a 26.1 (6)% minor component.

Related literature

For the structure of 2-bromonitrobenzene, see: Fronczek (2006 ). For the structure of 3-bromonitrobenzene, see: Charlton & Trotter (1963 ).

Experimental

Crystal data

C₆H₄BrNO₂
M_r = 202.01
Triclinic, $[P \overline 1]$
a = 6.3676 (6) Å
b = 7.3635 (7) Å
c = 7.6798 (7) Å
α = 65.554 (9)°
β = 87.705 (8)°
γ = 88.884 (8)°
V = 327.54 (5) Å³
Z = 2
Mo Kα radiation
μ = 6.20 mm⁻¹
T = 100 K
0.20 × 0.10 × 0.05 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.414, T_max = 1.000
2142 measured reflections
1443 independent reflections
1365 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.119
S = 1.07
1443 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.91 e Å⁻³
Δρ_min = −1.58 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱ	0.95	2.52	3.359 (6)	147
C5—H5⋯O2ⁱⁱ	0.95	2.54	3.276 (6)	135
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y, -z+2.

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811003394/xu5150sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003394/xu5150Isup2.hkl

checkCIF report

Comment top

4-Bromo-1-nitrobenzene (Scheme I) was synthesized as a precursor that will be used in the synthesis of 4,4'-bis(aminophenoxy)biphenyl (the compound is also commercially available: http://www.chemindustry.com/chemicals/815494.html). The molecule is flat (Fig. 1) as the nitro substituent is co-planar with the aromatic ring. π-π stacking occrs between parallel benzene rings of adjacent molecules, centroids distance between C1-ring and C1ⁱ-ring (symmetry code: (i) 1-x, -5, 1-z) is 3.643 (3) Å and that between C1-ring and C1ⁱⁱ-ring (symmetry code: (ii) 1-x, 1-y, 1-z) is 3.741 (3) Å. Intermolecular weak C—H···O hydrogen bonding (Table 1) and the short Br···O contacts [3.227 (4), 3.401 (4) Å] are observed in the crystal structure.

Related literature top

For the structure of 2-bromonitrobenzene, see: Fronczek (2006). For the structure of 3-bromonitrobenzene, see: Charlton & Trotter (1963).

Experimental top

The nitrating mixture cosisted of 5 ml conc. HNO₃ and 5 ml conc. H₂SO₄ kept at 273 K. Bromobenzene (2.6 ml) was added. The temperature was then raised to about 333 K for 3 h. The mixture was added to water (200 ml); the organic compound was extracted by using dichloromethane. The solvent was dried and then alllowed to evaporate to yield the product in 70% yield.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₆H₄BrNO₂ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

4-Bromo-1-nitrobenzene top

Crystal data top

C₆H₄BrNO₂	Z = 2
M_r = 202.01	F(000) = 196
Triclinic, P1	D_x = 2.048 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.3676 (6) Å	Cell parameters from 1590 reflections
b = 7.3635 (7) Å	θ = 2.9–28.3°
c = 7.6798 (7) Å	µ = 6.20 mm⁻¹
α = 65.554 (9)°	T = 100 K
β = 87.705 (8)°	Block, colorless
γ = 88.884 (8)°	0.20 × 0.10 × 0.05 mm
V = 327.54 (5) Å³

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1443 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1365 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.052
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.9°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −9→9
T_min = 0.414, T_max = 1.000	l = −9→9
2142 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0671P)² + 0.4717P] where P = (F_o² + 2F_c²)/3
1443 reflections	(Δ/σ)_max = 0.001
92 parameters	Δρ_max = 0.91 e Å⁻³
0 restraints	Δρ_min = −1.58 e Å⁻³

Crystal data top

C₆H₄BrNO₂	γ = 88.884 (8)°
M_r = 202.01	V = 327.54 (5) Å³
Triclinic, P1	Z = 2
a = 6.3676 (6) Å	Mo Kα radiation
b = 7.3635 (7) Å	µ = 6.20 mm⁻¹
c = 7.6798 (7) Å	T = 100 K
α = 65.554 (9)°	0.20 × 0.10 × 0.05 mm
β = 87.705 (8)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1443 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1365 reflections with I > 2σ(I)
T_min = 0.414, T_max = 1.000	R_int = 0.052
2142 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.07	Δρ_max = 0.91 e Å⁻³
1443 reflections	Δρ_min = −1.58 e Å⁻³
92 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.83556 (7)	0.24763 (7)	0.14671 (6)	0.01978 (19)
O1	0.0573 (5)	0.3167 (6)	0.7390 (5)	0.0238 (8)
O2	0.3071 (6)	0.2117 (6)	0.9389 (5)	0.0245 (8)
N1	0.2383 (6)	0.2623 (6)	0.7787 (5)	0.0151 (7)
C6	0.7151 (7)	0.1751 (7)	0.5288 (7)	0.0173 (9)
H6	0.8526	0.1212	0.5575	0.021*
C5	0.5810 (7)	0.1811 (7)	0.6722 (6)	0.0146 (9)
H5	0.6251	0.1326	0.8004	0.018*
C2	0.4465 (7)	0.3256 (7)	0.2969 (7)	0.0173 (9)
H2	0.4024	0.3750	0.1687	0.021*
C3	0.3121 (7)	0.3291 (7)	0.4408 (6)	0.0159 (9)
H3	0.1731	0.3792	0.4130	0.019*
C1	0.6478 (7)	0.2483 (6)	0.3429 (6)	0.0157 (9)
C4	0.3809 (7)	0.2594 (6)	0.6254 (6)	0.0125 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0204 (3)	0.0213 (3)	0.0206 (3)	−0.00244 (19)	0.00662 (18)	−0.0122 (2)
O1	0.0149 (16)	0.038 (2)	0.0232 (18)	0.0024 (15)	0.0001 (13)	−0.0174 (16)
O2	0.0299 (19)	0.032 (2)	0.0131 (16)	0.0028 (16)	−0.0003 (14)	−0.0107 (15)
N1	0.0173 (18)	0.0152 (18)	0.0156 (18)	−0.0013 (14)	0.0010 (14)	−0.0093 (15)
C6	0.015 (2)	0.017 (2)	0.021 (2)	−0.0008 (17)	0.0000 (17)	−0.0089 (19)
C5	0.016 (2)	0.015 (2)	0.014 (2)	0.0014 (16)	−0.0023 (16)	−0.0076 (17)
C2	0.020 (2)	0.018 (2)	0.016 (2)	−0.0004 (18)	0.0001 (17)	−0.0094 (18)
C3	0.018 (2)	0.016 (2)	0.015 (2)	0.0020 (17)	−0.0041 (17)	−0.0072 (17)
C1	0.019 (2)	0.014 (2)	0.019 (2)	−0.0005 (18)	0.0015 (18)	−0.0113 (19)
C4	0.0133 (19)	0.015 (2)	0.012 (2)	−0.0005 (16)	0.0005 (15)	−0.0090 (17)

Geometric parameters (Å, º) top

Br1—C1	1.887 (4)	C5—C4	1.387 (6)
O1—N1	1.220 (5)	C5—H5	0.9500
O2—N1	1.226 (5)	C2—C3	1.379 (6)
N1—C4	1.464 (5)	C2—C1	1.390 (6)
C6—C1	1.384 (6)	C2—H2	0.9500
C6—C5	1.381 (6)	C3—C4	1.380 (6)
C6—H6	0.9500	C3—H3	0.9500

O1—N1—O2	123.6 (4)	C1—C2—H2	120.6
O1—N1—C4	117.9 (4)	C4—C3—C2	119.6 (4)
O2—N1—C4	118.4 (4)	C4—C3—H3	120.2
C1—C6—C5	119.5 (4)	C2—C3—H3	120.2
C1—C6—H6	120.2	C6—C1—C2	121.5 (4)
C5—C6—H6	120.2	C6—C1—Br1	119.2 (3)
C4—C5—C6	118.7 (4)	C2—C1—Br1	119.3 (3)
C4—C5—H5	120.6	C3—C4—C5	121.8 (4)
C6—C5—H5	120.6	C3—C4—N1	119.7 (4)
C3—C2—C1	118.8 (4)	C5—C4—N1	118.4 (4)
C3—C2—H2	120.6

C1—C6—C5—C4	0.5 (7)	C2—C3—C4—N1	−179.8 (4)
C1—C2—C3—C4	1.1 (7)	C6—C5—C4—C3	0.7 (7)
C5—C6—C1—C2	−0.9 (7)	C6—C5—C4—N1	179.0 (4)
C5—C6—C1—Br1	177.9 (3)	O1—N1—C4—C3	4.1 (6)
C3—C2—C1—C6	0.1 (7)	O2—N1—C4—C3	−175.3 (4)
C3—C2—C1—Br1	−178.7 (3)	O1—N1—C4—C5	−174.3 (4)
C2—C3—C4—C5	−1.5 (7)	O2—N1—C4—C5	6.3 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.95	2.52	3.359 (6)	147
C5—H5···O2ⁱⁱ	0.95	2.54	3.276 (6)	135

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

Experimental details

Crystal data
Chemical formula	C₆H₄BrNO₂
M_r	202.01
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.3676 (6), 7.3635 (7), 7.6798 (7)
α, β, γ (°)	65.554 (9), 87.705 (8), 88.884 (8)
V (Å³)	327.54 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.20
Crystal size (mm)	0.20 × 0.10 × 0.05

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.414, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2142, 1443, 1365
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.119, 1.07
No. of reflections	1443
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.91, −1.58

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.95	2.52	3.359 (6)	147
C5—H5···O2ⁱⁱ	0.95	2.54	3.276 (6)	135

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

Acknowledgements

We thank the Higher Education Commission of Pakistan and the University of Malaya for supporting this study.

References

Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Charlton, T. L. & Trotter, J. (1963). Acta Cryst. 16, 313. CSD CrossRef IUCr Journals Web of Science Google Scholar
Fronczek, F. R. (2006). Private communication (refcode 264855). CCDC, Cambridge, England. Google Scholar
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