Crystal structure of 2-bromo-4,6-di­nitroaniline

Kang, G.; Kim, T.H.; Lee, E.-J.; Kang, C.H.

doi:10.1107/S2056989015017946

organic compounds

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ISSN: 2056-9890

Volume 71| Part 11| November 2015| Page o813

https://doi.org/10.1107/S2056989015017946

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Crystal structure of 2-bromo-4,6-dinitroaniline

Gihaeng Kang,^a Tae Ho Kim,^a ^* Eui-Jae Lee ^b and Chang Ho Kang ^c ^*

^aDepartment of Chemistry and Research Institute of Natural Sciences, Gyeongsang, National University, Jinju 52828, Republic of Korea, ^bResearch Center at Kyung-In Synthetic Corporation (KISCO), Yangcheon-ro 75-69, Gangseo-gu, Seoul 07517, Republic of Korea, and ^cDivision of Applied Life Science and PMBBRC, Gyeongsang, National University, Jinju 52828, Republic of Korea
^*Correspondence e-mail: thkim@gnu.ac.kr, jacobgnu69@gnu.ac.kr

Edited by J. Simpson, University of Otago, New Zealand (Received 18 September 2015; accepted 25 September 2015; online 3 October 2015)

In the title compound, C₆H₄BrN₃O₄, the dihedral angles between the nitro groups and the aniline ring are 2.04 (3) and 1.18 (4)°, respectively. In the crystal, N—H⋯O and C—H⋯O hydrogen bonds and weak side-on C—Br⋯π interactions [3.5024 (12) Å] link adjacent molecules, forming a three-dimensional network. A close O⋯Br contact [3.259 (2) Å] may also add additional stability.

Keywords: crystal structure; aniline derivative; hydrogen bonding; C—Br⋯π interactions.

CCDC reference: 1427403

1. Related literature

For information on the title compound, see: Yadav & Sharma (2010 ). For a related crystal structure, see: Glidewell et al. (2002 ).

2. Experimental

2.1. Crystal data

C₆H₄BrN₃O₄
M_r = 262.03
Monoclinic P 2₁ /n
a = 6.6955 (2) Å
b = 7.7720 (2) Å
c = 16.0608 (4) Å
β = 95.4182 (14)°
V = 832.03 (4) Å³
Z = 4
Mo Kα radiation
μ = 4.93 mm⁻¹
T = 173 K
0.20 × 0.15 × 0.08 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ) T_min = 0.534, T_max = 0.746
12322 measured reflections
1892 independent reflections
1648 reflections with I > 2σ(I)
R_int = 0.030

2.3. Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.083
S = 1.06
1892 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.85 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.88	2.16	2.893 (3)	141
N1—H1B⋯O4ⁱⁱ	0.88	2.36	3.139 (4)	148
C5—H5⋯O1ⁱⁱⁱ	0.95	2.55	3.209 (4)	127
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x-1, -y+2, -z+2; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ); molecular graphics: DIAMOND (Brandenburg, 2010 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

CCDC reference: 1427403

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989015017946/sj5477sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015017946/sj5477Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015017946/sj5477Isup3.cml

checkCIF report

Comment top

The title compound, C₆H₄BrN₃O₄, is an aniline derivative with additional bromine and nitro substituents. Aniline is the simplest of the primary aromatic amines an organic base used, as are its derivatives, to make dyes, drugs, explosives, plastics and chemicals for the rubber industry (Yadav & Sharma, 2010). Its crystal structure is reported herein. In this compound (Fig. 1), the dihedral angles between the nitro groups and the aniline ring are 2.04 (3) and 1.18 (4)°, respectively. All bond lengths and bond angles are normal and comparable to those observed in the crystal structure of a similar compound (Glidewell et al., 2002).

The crystal structure (Fig. 2) is stabilized by N—H···O and C—H···O hydrogen bonds (Table 1), as well as an intermolecular side-on C2—Br1···Cg1^iv interaction [Br1···Cg = 3.5024 (12) Å, C2—Br1···Cg = 96.90 (9) °] (Cg1 is the centroid of the C1–C6 ring) [symmetry code: (iv), -x, -y + 1, -z + 2]. A close O3···Br1^iv contact, 3.259 (2) Å may also contribute, iv = -1/2+x,1.5-y, -1/2+z. These contacts result in a three-dimensional network.

Related literature top

For information on the title compound, see: Yadav & Sharma (2010). For a related crystal structure, see: Glidewell et al. (2002).

Experimental top

The title compound was supplied by the Kyung In Synthetic Corporation. Slow evaporation of a solution in CH₂Cl₂ gave single crystals suitable for X-ray analysis.

Structure description top

For information on the title compound, see: Yadav & Sharma (2010). For a related crystal structure, see: Glidewell et al. (2002).

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.
	Fig. 2. Crystal packing viewed along the a axis. The intermolecular interactions are shown as dashed lines.

2-Bromo-4,6-dinitroaniline top

Crystal data top

C₆H₄BrN₃O₄	F(000) = 512
M_r = 262.03	D_x = 2.092 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.6955 (2) Å	Cell parameters from 6099 reflections
b = 7.7720 (2) Å	θ = 2.6–27.1°
c = 16.0608 (4) Å	µ = 4.93 mm⁻¹
β = 95.4182 (14)°	T = 173 K
V = 832.03 (4) Å³	Block, yellow
Z = 4	0.20 × 0.15 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	1648 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.030
Absorption correction: multi-scan (SADABS; Bruker, 2013)	θ_max = 27.5°, θ_min = 2.6°
T_min = 0.534, T_max = 0.746	h = −8→8
12322 measured reflections	k = −10→10
1892 independent reflections	l = −20→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0334P)² + 1.6027P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
1892 reflections	Δρ_max = 0.85 e Å⁻³
127 parameters	Δρ_min = −0.51 e Å⁻³

Crystal data top

C₆H₄BrN₃O₄	V = 832.03 (4) Å³
M_r = 262.03	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.6955 (2) Å	µ = 4.93 mm⁻¹
b = 7.7720 (2) Å	T = 173 K
c = 16.0608 (4) Å	0.20 × 0.15 × 0.08 mm
β = 95.4182 (14)°

Data collection top

Bruker APEXII CCD diffractometer	1892 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	1648 reflections with I > 2σ(I)
T_min = 0.534, T_max = 0.746	R_int = 0.030
12322 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.06	Δρ_max = 0.85 e Å⁻³
1892 reflections	Δρ_min = −0.51 e Å⁻³
127 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Br1	0.19258 (6)	0.64018 (4)	1.10024 (2)	0.04116 (14)
O1	0.4575 (4)	0.6238 (3)	0.79915 (19)	0.0484 (7)
O2	0.2420 (4)	0.7493 (4)	0.71047 (15)	0.0544 (8)
O3	−0.3569 (3)	0.9745 (3)	0.79238 (13)	0.0379 (5)
O4	−0.4360 (3)	0.9614 (3)	0.91874 (15)	0.0397 (6)
N1	−0.1949 (4)	0.8183 (4)	1.03776 (15)	0.0327 (6)
H1A	−0.1531	0.7837	1.0886	0.039*
H1B	−0.3120	0.8696	1.0282	0.039*
N2	0.2978 (4)	0.6977 (4)	0.78113 (17)	0.0348 (6)
N3	−0.3276 (3)	0.9358 (3)	0.86609 (13)	0.0212 (5)
C1	−0.0806 (4)	0.7930 (4)	0.97511 (16)	0.0230 (6)
C2	0.1093 (4)	0.7101 (4)	0.98987 (17)	0.0256 (6)
C3	0.2302 (4)	0.6777 (4)	0.92827 (19)	0.0277 (6)
H3	0.3551	0.6208	0.9404	0.033*
C4	0.1671 (4)	0.7299 (4)	0.84695 (18)	0.0263 (6)
C5	−0.0114 (4)	0.8115 (4)	0.82743 (17)	0.0233 (6)
H5	−0.0513	0.8456	0.7715	0.028*
C6	−0.1333 (4)	0.8435 (3)	0.89051 (16)	0.0214 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0571 (2)	0.0375 (2)	0.02593 (18)	−0.01145 (16)	−0.01191 (14)	0.00718 (13)
O1	0.0422 (14)	0.0411 (14)	0.0655 (18)	0.0096 (11)	0.0239 (13)	−0.0063 (12)
O2	0.0471 (15)	0.094 (2)	0.0241 (12)	−0.0027 (15)	0.0165 (11)	−0.0089 (13)
O3	0.0415 (13)	0.0450 (14)	0.0268 (11)	0.0051 (11)	0.0004 (10)	0.0036 (10)
O4	0.0329 (12)	0.0438 (14)	0.0437 (14)	0.0057 (10)	0.0111 (11)	0.0000 (11)
N1	0.0409 (15)	0.0416 (15)	0.0168 (11)	−0.0026 (12)	0.0096 (11)	−0.0002 (11)
N2	0.0351 (15)	0.0381 (15)	0.0340 (15)	−0.0082 (12)	0.0174 (12)	−0.0124 (12)
N3	0.0269 (12)	0.0220 (11)	0.0147 (10)	−0.0105 (9)	0.0011 (9)	0.0003 (9)
C1	0.0323 (15)	0.0214 (13)	0.0156 (12)	−0.0095 (11)	0.0051 (11)	−0.0032 (10)
C2	0.0339 (15)	0.0246 (14)	0.0175 (13)	−0.0095 (12)	−0.0025 (11)	0.0019 (11)
C3	0.0274 (14)	0.0242 (14)	0.0308 (15)	−0.0045 (11)	−0.0010 (12)	−0.0003 (12)
C4	0.0290 (15)	0.0289 (15)	0.0224 (13)	−0.0054 (12)	0.0100 (12)	−0.0058 (11)
C5	0.0276 (14)	0.0274 (14)	0.0153 (12)	−0.0069 (11)	0.0046 (11)	−0.0009 (10)
C6	0.0257 (13)	0.0218 (13)	0.0170 (12)	−0.0045 (11)	0.0031 (10)	−0.0019 (10)

Geometric parameters (Å, º) top

Br1—C2	1.887 (3)	N3—C6	1.505 (4)
O1—N2	1.224 (4)	C1—C2	1.425 (4)
O2—N2	1.228 (4)	C1—C6	1.426 (4)
O3—N3	1.219 (3)	C2—C3	1.360 (4)
O4—N3	1.182 (3)	C3—C4	1.395 (4)
N1—C1	1.335 (4)	C3—H3	0.9500
N1—H1A	0.8800	C4—C5	1.363 (4)
N1—H1B	0.8800	C5—C6	1.382 (4)
N2—C4	1.456 (4)	C5—H5	0.9500

C1—N1—H1A	120.0	C1—C2—Br1	117.8 (2)
C1—N1—H1B	120.0	C2—C3—C4	118.6 (3)
H1A—N1—H1B	120.0	C2—C3—H3	120.7
O1—N2—O2	123.7 (3)	C4—C3—H3	120.7
O1—N2—C4	118.7 (3)	C5—C4—C3	122.2 (3)
O2—N2—C4	117.6 (3)	C5—C4—N2	119.1 (3)
O4—N3—O3	126.8 (3)	C3—C4—N2	118.7 (3)
O4—N3—C6	117.9 (2)	C4—C5—C6	118.7 (3)
O3—N3—C6	115.3 (2)	C4—C5—H5	120.6
N1—C1—C2	120.5 (3)	C6—C5—H5	120.6
N1—C1—C6	124.7 (3)	C5—C6—C1	122.6 (3)
C2—C1—C6	114.8 (2)	C5—C6—N3	116.8 (2)
C3—C2—C1	123.1 (3)	C1—C6—N3	120.6 (2)
C3—C2—Br1	119.1 (2)

N1—C1—C2—C3	178.6 (3)	C3—C4—C5—C6	0.1 (4)
C6—C1—C2—C3	−1.3 (4)	N2—C4—C5—C6	−179.2 (3)
N1—C1—C2—Br1	−0.5 (4)	C4—C5—C6—C1	−0.7 (4)
C6—C1—C2—Br1	179.52 (19)	C4—C5—C6—N3	179.3 (2)
C1—C2—C3—C4	0.9 (4)	N1—C1—C6—C5	−178.7 (3)
Br1—C2—C3—C4	180.0 (2)	C2—C1—C6—C5	1.3 (4)
C2—C3—C4—C5	−0.2 (4)	N1—C1—C6—N3	1.3 (4)
C2—C3—C4—N2	179.1 (3)	C2—C1—C6—N3	−178.7 (2)
O1—N2—C4—C5	−179.7 (3)	O4—N3—C6—C5	178.5 (3)
O2—N2—C4—C5	1.4 (4)	O3—N3—C6—C5	−0.6 (3)
O1—N2—C4—C3	1.0 (4)	O4—N3—C6—C1	−1.5 (4)
O2—N2—C4—C3	−177.9 (3)	O3—N3—C6—C1	179.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.88	2.16	2.893 (3)	141
N1—H1B···O4ⁱⁱ	0.88	2.36	3.139 (4)	148
C5—H5···O1ⁱⁱⁱ	0.95	2.55	3.209 (4)	127

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x−1, −y+2, −z+2; (iii) −x+1/2, y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.88	2.16	2.893 (3)	141.0
N1—H1B···O4ⁱⁱ	0.88	2.36	3.139 (4)	147.6
C5—H5···O1ⁱⁱⁱ	0.95	2.55	3.209 (4)	126.8

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x−1, −y+2, −z+2; (iii) −x+1/2, y+1/2, −z+3/2.

Acknowledgements

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 2015R1D1A4A01020317).

References

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