4-Bromo-1-nitro­benzene

Abstract

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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 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

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 ▶).

Supplementary Material

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

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

Carbon-bound H-atoms were placed in calculated positions [C—H 0.95 Å, U_iso(H) 1.2U_eq(C)] and were included in the refinement in the riding model approximation.

The crystal is a non-merohedral twin; the separation of the two domains was effected by CrysAlis PRO (Agilent, 2010).

Figures

Fig. 1.

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

Crystal data

C6H4BrNO2	Z = 2
Mr = 202.01	F(000) = 196
Triclinic, P1	Dx = 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

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	Rint = 0.052
Detector resolution: 10.4041 pixels mm-1	θmax = 27.5°, θmin = 2.9°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −9→9
Tmin = 0.414, Tmax = 1.000	l = −9→9
2142 measured reflections

Refinement

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(Fo2) + (0.0671P)2 + 0.4717P] where P = (Fo2 + 2Fc2)/3
1443 reflections	(Δ/σ)max = 0.001
92 parameters	Δρmax = 0.91 e Å−3
0 restraints	Δρmin = −1.58 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.