2-Bromo-4-nitro­aniline

Arshad, M.N.; Tahir, M.N.; Khan, I.U.; Shafiq, M.

doi:10.1107/S1600536809004073

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o480

doi:10.1107/S1600536809004073

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2-Bromo-4-nitroaniline

Muhammad Nadeem Arshad,^a M. Nawaz Tahir,^b ^* Islam Ullah Khan ^a and Muhammad Shafiq ^a

^aDepartment of Chemistry, Government College University, Lahore, Pakistan, and ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 1 February 2009; accepted 3 February 2009; online 6 February 2009)

In the molecule of the title compound, C₆H₅BrN₂O₂, the dihedral angle between the nitro group and the aromatic ring is 4.57 (4)°. An intramolecular N—H⋯Br interaction results in the formation of a planar five-membered ring, which is oriented with respect to the aromatic ring at a dihedral angle of 1.64 (6)°. In the crystal structure, intermolecular N—H⋯N and N—H⋯O hydrogen bonds link the molecules.

Related literature

For related structures, see: Arshad et al. (2008 , 2009 ); McPhail & Sim (1965 ); McWilliam et al. (2001 ); Krishna Mohan et al. (2004 ).

Experimental

Crystal data

C₆H₅BrN₂O₂
M_r = 217.03
Orthorhombic, P n a 2₁
a = 11.098 (3) Å
b = 16.763 (4) Å
c = 3.9540 (9) Å
V = 735.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 5.53 mm⁻¹
T = 296 (2) K
0.26 × 0.12 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.450, T_max = 0.578
4932 measured reflections
1542 independent reflections
986 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.092
S = 1.00
1542 reflections
100 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.62 e Å⁻³
Absolute structure: Flack (1983 ), 469 Friedel pairs
Flack parameter: 0.01 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N1ⁱ	0.86	2.32	3.158 (7)	167.00
N1—H1B⋯Br1	0.86	2.68	3.095 (5)	111.00
N1—H1B⋯O2ⁱⁱ	0.86	2.32	3.049 (7)	143.00
Symmetry codes: (i) $[-x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809004073/hk2621sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809004073/hk2621Isup2.hkl

checkCIF report

Comment top

The title compound, (I), has been prepared as an intermediate for the synthesis of sulfonamides (Arshad et al., 2009) and benzothiazines (Arshad et al., 2008).

The crystal structures of 2-iodo-4-nitroaniline, (II) (McWilliam et al., 2001) and 2-chloro-4-nitroaniline, (III) (McPhail & Sim, 1965) have been reported. The title compound, (I), (Fig 1) is structural isomer of (III). It is essentially planar. The dihedral angle between the nitro group (O1/O2/N2) and the aromatic ring A (C1-C6) is 4.57 (4)°. The intramolecular N-H···Br interaction (Table 1) results in the formation of a planar five-membered ring (Br1/N1/C3/C4/H1B), which is oriented with respect to ring A at a dihedral angle of 1.64 (6)°. So, they are nearly coplanar.

In the crystal structure, intermolecular N-H···N and N-H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For related structures, see: Arshad et al. (2008, 2009); McPhail & Sim (1965); McWilliam et al. (2001); Krishna Mohan et al. (2004).

Experimental top

The title compound was synthesized following the method available in literature (Krishna Mohan et al., 2004). 4-Nitro aniline (6 g, 0.0435 mol) and ammonium bromide (4.5 g, 0.0479 mol) were charged to a flask (50 ml) containing acetic acid (30 ml). Hydrogen peroxide (1.629 g, 0.0479 mol, 35%) was added dropwise to the mixture, and stirred at room temperature for 3 h. Then, the obtained precipitate was filtered and washed with water and recrystallized in dichloromethane and methanol.

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 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bond is shown as dashed line.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

2-Bromo-4-nitroaniline top

Crystal data top

C₆H₅BrN₂O₂	F(000) = 424
M_r = 217.03	D_x = 1.960 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 1542 reflections
a = 11.098 (3) Å	θ = 3.1–28.6°
b = 16.763 (4) Å	µ = 5.53 mm⁻¹
c = 3.9540 (9) Å	T = 296 K
V = 735.6 (3) Å³	Needle, yellow
Z = 4	0.26 × 0.12 × 0.10 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1542 independent reflections
Radiation source: fine-focus sealed tube	986 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
Detector resolution: 7.40 pixels mm^-1	θ_max = 28.6°, θ_min = 3.1°
ω scans	h = −13→14
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −22→22
T_min = 0.450, T_max = 0.578	l = −3→5
4932 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0302P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
1542 reflections	Δρ_max = 0.50 e Å⁻³
100 parameters	Δρ_min = −0.62 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 469 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (2)

Crystal data top

C₆H₅BrN₂O₂	V = 735.6 (3) Å³
M_r = 217.03	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 11.098 (3) Å	µ = 5.53 mm⁻¹
b = 16.763 (4) Å	T = 296 K
c = 3.9540 (9) Å	0.26 × 0.12 × 0.10 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1542 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	986 reflections with I > 2σ(I)
T_min = 0.450, T_max = 0.578	R_int = 0.058
4932 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.092	Δρ_max = 0.50 e Å⁻³
S = 1.00	Δρ_min = −0.62 e Å⁻³
1542 reflections	Absolute structure: Flack (1983), 469 Friedel pairs
100 parameters	Absolute structure parameter: 0.01 (2)
1 restraint

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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) top

	x	y	z	U_iso*/U_eq
Br1	0.34261 (5)	0.56438 (3)	0.7237 (2)	0.0524 (2)
O1	0.4834 (5)	0.2673 (3)	0.5214 (15)	0.088 (3)
O2	0.3637 (4)	0.1882 (2)	0.763 (3)	0.101 (2)
N1	0.1095 (4)	0.5118 (3)	1.0912 (13)	0.0510 (18)
N2	0.3960 (5)	0.2544 (3)	0.689 (2)	0.064 (2)
C1	0.3231 (4)	0.3212 (3)	0.8007 (18)	0.043 (3)
C2	0.3615 (4)	0.3974 (3)	0.730 (3)	0.0420 (17)
C3	0.2913 (5)	0.4600 (3)	0.8270 (13)	0.0347 (19)
C4	0.1833 (5)	0.4491 (3)	0.9987 (15)	0.0377 (17)
C5	0.1479 (5)	0.3705 (4)	1.0711 (16)	0.048 (2)
C6	0.2169 (5)	0.3076 (3)	0.9745 (17)	0.051 (2)
H1A	0.04332	0.50258	1.19738	0.0611*
H1B	0.12976	0.55993	1.04260	0.0611*
H2	0.43405	0.40604	0.61823	0.0502*
H5	0.07627	0.36137	1.18676	0.0576*
H6	0.19297	0.25579	1.02478	0.0605*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0557 (3)	0.0436 (3)	0.0578 (4)	−0.0094 (3)	−0.0026 (7)	0.0100 (5)
O1	0.075 (4)	0.077 (4)	0.112 (5)	0.028 (3)	0.016 (4)	−0.009 (3)
O2	0.110 (4)	0.037 (2)	0.157 (6)	0.010 (2)	0.000 (5)	−0.006 (5)
N1	0.035 (2)	0.056 (3)	0.062 (4)	0.001 (2)	0.003 (2)	−0.008 (2)
N2	0.063 (3)	0.051 (3)	0.078 (5)	0.017 (3)	−0.018 (5)	−0.007 (5)
C1	0.041 (3)	0.046 (3)	0.041 (7)	0.001 (2)	−0.010 (3)	0.000 (3)
C2	0.034 (3)	0.049 (3)	0.043 (3)	−0.001 (2)	0.005 (5)	0.009 (6)
C3	0.034 (3)	0.037 (3)	0.033 (4)	−0.007 (2)	−0.007 (2)	0.002 (2)
C4	0.038 (3)	0.049 (3)	0.026 (3)	−0.002 (3)	−0.012 (3)	0.000 (3)
C5	0.043 (3)	0.053 (4)	0.047 (4)	−0.015 (3)	0.002 (3)	0.006 (3)
C6	0.056 (4)	0.037 (3)	0.059 (5)	−0.008 (3)	−0.018 (4)	0.005 (3)

Geometric parameters (Å, º) top

Br1—C3	1.885 (5)	C1—C2	1.375 (7)
O1—N2	1.195 (9)	C2—C3	1.362 (8)
O2—N2	1.202 (7)	C3—C4	1.390 (8)
N1—C4	1.382 (7)	C4—C5	1.404 (8)
N2—C1	1.450 (8)	C5—C6	1.358 (8)
N1—H1B	0.8600	C2—H2	0.9300
N1—H1A	0.8600	C5—H5	0.9300
C1—C6	1.383 (8)	C6—H6	0.9300

Br1···N1	3.095 (5)	C5···C1^ix	3.576 (9)
Br1···H1B	2.6800	C5···C2^ix	3.551 (11)
Br1···H2ⁱ	2.9700	C6···C1^ix	3.480 (10)
O1···C6ⁱⁱ	3.391 (8)	C6···O1^x	3.391 (8)
O2···N1ⁱⁱⁱ	3.049 (7)	C4···H1A^v	2.9000
O1···H2	2.4200	H1A···H5	2.4000
O1···H5^iv	2.7300	H1A···N1^v	2.9500
O2···H6	2.4400	H1A···N1^vi	2.3200
O2···H1Bⁱⁱⁱ	2.3200	H1A···C4^vi	2.9000
N1···Br1	3.095 (5)	H1A···H1A^v	2.2000
N1···N1^v	3.158 (7)	H1A···H1A^vi	2.2000
N1···N1^vi	3.158 (7)	H1A···H1B^vi	2.5800
N1···O2^vii	3.049 (7)	H1B···Br1	2.6800
N1···H1A^v	2.3200	H1B···H1A^v	2.5800
N1···H1A^vi	2.9500	H1B···O2^vii	2.3200
C1···C5^viii	3.576 (9)	H2···O1	2.4200
C1···C6^viii	3.480 (10)	H2···Br1^xi	2.9700
C2···C5^viii	3.551 (11)	H5···H1A	2.4000
C3···C4^viii	3.492 (8)	H5···O1^xii	2.7300
C4···C3^ix	3.492 (8)	H6···O2	2.4400

O1—N2—O2	123.0 (6)	C2—C3—C4	122.0 (5)
O1—N2—C1	118.8 (5)	N1—C4—C5	119.6 (5)
O2—N2—C1	118.2 (6)	N1—C4—C3	122.7 (5)
H1A—N1—H1B	120.00	C3—C4—C5	117.7 (5)
C4—N1—H1A	120.00	C4—C5—C6	120.9 (5)
C4—N1—H1B	120.00	C1—C6—C5	119.5 (5)
N2—C1—C6	120.0 (5)	C1—C2—H2	121.00
N2—C1—C2	118.8 (5)	C3—C2—H2	121.00
C2—C1—C6	121.2 (5)	C4—C5—H5	120.00
C1—C2—C3	118.8 (6)	C6—C5—H5	120.00
Br1—C3—C2	118.8 (4)	C1—C6—H6	120.00
Br1—C3—C4	119.2 (4)	C5—C6—H6	120.00

O1—N2—C1—C2	−4.5 (11)	C1—C2—C3—C4	0.9 (12)
O1—N2—C1—C6	175.4 (7)	Br1—C3—C4—N1	1.6 (8)
O2—N2—C1—C2	177.4 (9)	Br1—C3—C4—C5	179.9 (4)
O2—N2—C1—C6	−2.8 (11)	C2—C3—C4—N1	−178.3 (7)
N2—C1—C2—C3	178.2 (7)	C2—C3—C4—C5	0.1 (10)
C6—C1—C2—C3	−1.6 (13)	N1—C4—C5—C6	178.1 (6)
N2—C1—C6—C5	−178.5 (6)	C3—C4—C5—C6	−0.3 (9)
C2—C1—C6—C5	1.4 (11)	C4—C5—C6—C1	−0.4 (10)
C1—C2—C3—Br1	−179.0 (6)

Symmetry codes: (i) −x+1, −y+1, z+1/2; (ii) x+1/2, −y+1/2, z; (iii) −x+1/2, y−1/2, z−1/2; (iv) x+1/2, −y+1/2, z−1; (v) −x, −y+1, z−1/2; (vi) −x, −y+1, z+1/2; (vii) −x+1/2, y+1/2, z+1/2; (viii) x, y, z−1; (ix) x, y, z+1; (x) x−1/2, −y+1/2, z; (xi) −x+1, −y+1, z−1/2; (xii) x−1/2, −y+1/2, z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N1^vi	0.86	2.32	3.158 (7)	167.00
N1—H1B···Br1	0.86	2.68	3.095 (5)	111.00
N1—H1B···O2^vii	0.86	2.32	3.049 (7)	143.00

Symmetry codes: (vi) −x, −y+1, z+1/2; (vii) −x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₆H₅BrN₂O₂
M_r	217.03
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	296
a, b, c (Å)	11.098 (3), 16.763 (4), 3.9540 (9)
V (Å³)	735.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.53
Crystal size (mm)	0.26 × 0.12 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.450, 0.578
No. of measured, independent and observed [I > 2σ(I)] reflections	4932, 1542, 986
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.674

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.092, 1.00
No. of reflections	1542
No. of parameters	100
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.62
Absolute structure	Flack (1983), 469 Friedel pairs
Absolute structure parameter	0.01 (2)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N1ⁱ	0.86	2.32	3.158 (7)	167.00
N1—H1B···Br1	0.86	2.68	3.095 (5)	111.00
N1—H1B···O2ⁱⁱ	0.86	2.32	3.049 (7)	143.00

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

Acknowledgements

MNA greatfully acknowledges the Higher Education Commission, Islamabad, Pakistan, for providing him with a Scholarship under the Indigenous PhD Program (PIN 042–120607-PS2–183).

References

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