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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015017946/sj5477sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2056989015017946/sj5477Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989015017946/sj5477Isup3.cml
Supplementary material

CCDC reference: 1427403

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.033
  • wR factor = 0.083
  • Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT430_ALERT_2_C Short Inter D...A Contact O4 .. O4 .. 2.89 Ang. PLAT431_ALERT_2_C Short Inter HL..A Contact Br1 .. O3 .. 3.26 Ang.
Alert level G PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 2 Report PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 3 Note
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 2 ALERT level C = Check. Ensure it is not caused by an omission or oversight 2 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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···Cg1iv 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···Br1iv 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.

Refinement top

All H-atoms were positioned geometrically and refined using a riding model with d(N—H) = 0.88 Å, Uiso = 1.2Ueq(C) for amine group, d(C—H) = 0.95 Å, Uiso = 1.2Ueq(C) for aromatic C—H.

Structure description 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···Cg1iv 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···Br1iv 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.

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
[Figure 1] 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.
[Figure 2] 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
C6H4BrN3O4F(000) = 512
Mr = 262.03Dx = 2.092 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.6955 (2) ÅCell parameters from 6099 reflections
b = 7.7720 (2) Åθ = 2.6–27.1°
c = 16.0608 (4) ŵ = 4.93 mm1
β = 95.4182 (14)°T = 173 K
V = 832.03 (4) Å3Block, yellow
Z = 40.20 × 0.15 × 0.08 mm
Data collection top
Bruker APEXII CCD
diffractometer
1648 reflections with I > 2σ(I)
φ and ω scansRint = 0.030
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
θmax = 27.5°, θmin = 2.6°
Tmin = 0.534, Tmax = 0.746h = 88
12322 measured reflectionsk = 1010
1892 independent reflectionsl = 2020
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.083 w = 1/[σ2(Fo2) + (0.0334P)2 + 1.6027P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.002
1892 reflectionsΔρmax = 0.85 e Å3
127 parametersΔρmin = 0.51 e Å3
Crystal data top
C6H4BrN3O4V = 832.03 (4) Å3
Mr = 262.03Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.6955 (2) ŵ = 4.93 mm1
b = 7.7720 (2) ÅT = 173 K
c = 16.0608 (4) Å0.20 × 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)
Tmin = 0.534, Tmax = 0.746Rint = 0.030
12322 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.083H-atom parameters constrained
S = 1.06Δρmax = 0.85 e Å3
1892 reflectionsΔρmin = 0.51 e Å3
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
xyzUiso*/Ueq
Br10.19258 (6)0.64018 (4)1.10024 (2)0.04116 (14)
O10.4575 (4)0.6238 (3)0.79915 (19)0.0484 (7)
O20.2420 (4)0.7493 (4)0.71047 (15)0.0544 (8)
O30.3569 (3)0.9745 (3)0.79238 (13)0.0379 (5)
O40.4360 (3)0.9614 (3)0.91874 (15)0.0397 (6)
N10.1949 (4)0.8183 (4)1.03776 (15)0.0327 (6)
H1A0.15310.78371.08860.039*
H1B0.31200.86961.02820.039*
N20.2978 (4)0.6977 (4)0.78113 (17)0.0348 (6)
N30.3276 (3)0.9358 (3)0.86609 (13)0.0212 (5)
C10.0806 (4)0.7930 (4)0.97511 (16)0.0230 (6)
C20.1093 (4)0.7101 (4)0.98987 (17)0.0256 (6)
C30.2302 (4)0.6777 (4)0.92827 (19)0.0277 (6)
H30.35510.62080.94040.033*
C40.1671 (4)0.7299 (4)0.84695 (18)0.0263 (6)
C50.0114 (4)0.8115 (4)0.82743 (17)0.0233 (6)
H50.05130.84560.77150.028*
C60.1333 (4)0.8435 (3)0.89051 (16)0.0214 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0571 (2)0.0375 (2)0.02593 (18)0.01145 (16)0.01191 (14)0.00718 (13)
O10.0422 (14)0.0411 (14)0.0655 (18)0.0096 (11)0.0239 (13)0.0063 (12)
O20.0471 (15)0.094 (2)0.0241 (12)0.0027 (15)0.0165 (11)0.0089 (13)
O30.0415 (13)0.0450 (14)0.0268 (11)0.0051 (11)0.0004 (10)0.0036 (10)
O40.0329 (12)0.0438 (14)0.0437 (14)0.0057 (10)0.0111 (11)0.0000 (11)
N10.0409 (15)0.0416 (15)0.0168 (11)0.0026 (12)0.0096 (11)0.0002 (11)
N20.0351 (15)0.0381 (15)0.0340 (15)0.0082 (12)0.0174 (12)0.0124 (12)
N30.0269 (12)0.0220 (11)0.0147 (10)0.0105 (9)0.0011 (9)0.0003 (9)
C10.0323 (15)0.0214 (13)0.0156 (12)0.0095 (11)0.0051 (11)0.0032 (10)
C20.0339 (15)0.0246 (14)0.0175 (13)0.0095 (12)0.0025 (11)0.0019 (11)
C30.0274 (14)0.0242 (14)0.0308 (15)0.0045 (11)0.0010 (12)0.0003 (12)
C40.0290 (15)0.0289 (15)0.0224 (13)0.0054 (12)0.0100 (12)0.0058 (11)
C50.0276 (14)0.0274 (14)0.0153 (12)0.0069 (11)0.0046 (11)0.0009 (10)
C60.0257 (13)0.0218 (13)0.0170 (12)0.0045 (11)0.0031 (10)0.0019 (10)
Geometric parameters (Å, º) top
Br1—C21.887 (3)N3—C61.505 (4)
O1—N21.224 (4)C1—C21.425 (4)
O2—N21.228 (4)C1—C61.426 (4)
O3—N31.219 (3)C2—C31.360 (4)
O4—N31.182 (3)C3—C41.395 (4)
N1—C11.335 (4)C3—H30.9500
N1—H1A0.8800C4—C51.363 (4)
N1—H1B0.8800C5—C61.382 (4)
N2—C41.456 (4)C5—H50.9500
C1—N1—H1A120.0C1—C2—Br1117.8 (2)
C1—N1—H1B120.0C2—C3—C4118.6 (3)
H1A—N1—H1B120.0C2—C3—H3120.7
O1—N2—O2123.7 (3)C4—C3—H3120.7
O1—N2—C4118.7 (3)C5—C4—C3122.2 (3)
O2—N2—C4117.6 (3)C5—C4—N2119.1 (3)
O4—N3—O3126.8 (3)C3—C4—N2118.7 (3)
O4—N3—C6117.9 (2)C4—C5—C6118.7 (3)
O3—N3—C6115.3 (2)C4—C5—H5120.6
N1—C1—C2120.5 (3)C6—C5—H5120.6
N1—C1—C6124.7 (3)C5—C6—C1122.6 (3)
C2—C1—C6114.8 (2)C5—C6—N3116.8 (2)
C3—C2—C1123.1 (3)C1—C6—N3120.6 (2)
C3—C2—Br1119.1 (2)
N1—C1—C2—C3178.6 (3)C3—C4—C5—C60.1 (4)
C6—C1—C2—C31.3 (4)N2—C4—C5—C6179.2 (3)
N1—C1—C2—Br10.5 (4)C4—C5—C6—C10.7 (4)
C6—C1—C2—Br1179.52 (19)C4—C5—C6—N3179.3 (2)
C1—C2—C3—C40.9 (4)N1—C1—C6—C5178.7 (3)
Br1—C2—C3—C4180.0 (2)C2—C1—C6—C51.3 (4)
C2—C3—C4—C50.2 (4)N1—C1—C6—N31.3 (4)
C2—C3—C4—N2179.1 (3)C2—C1—C6—N3178.7 (2)
O1—N2—C4—C5179.7 (3)O4—N3—C6—C5178.5 (3)
O2—N2—C4—C51.4 (4)O3—N3—C6—C50.6 (3)
O1—N2—C4—C31.0 (4)O4—N3—C6—C11.5 (4)
O2—N2—C4—C3177.9 (3)O3—N3—C6—C1179.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.882.162.893 (3)141
N1—H1B···O4ii0.882.363.139 (4)148
C5—H5···O1iii0.952.553.209 (4)127
Symmetry codes: (i) x1/2, y+3/2, z+1/2; (ii) x1, y+2, z+2; (iii) x+1/2, y+1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.882.162.893 (3)141.0
N1—H1B···O4ii0.882.363.139 (4)147.6
C5—H5···O1iii0.952.553.209 (4)126.8
Symmetry codes: (i) x1/2, y+3/2, z+1/2; (ii) x1, y+2, z+2; (iii) x+1/2, y+1/2, z+3/2.
 

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