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All interatomic distances in the title compound, C6H3BrN2O4, previously reported by Watson [Nature (London) (1960), 188, 1102–1103] and Gopalakrishna [Acta Cryst. (1969), A25, S-150], can be considered to be normal. The benzene ring is very slightly distorted from planarity. The weighted least-squares planes calculated through the atoms of the nitro groups make angles of 42.3 (3) and 9.7 (3)° with the benzene ring plane, for the 2- and 4-nitro groups, respectively. In the crystal, one weak C—H...O intermolecular hydrogen bond and two stacking interactions can be found. The structure is assembled into a three-dimensional net via these interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802005718/bt6132sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802005718/bt6132Isup2.hkl
Contains datablock I

CCDC reference: 185768

Key indicators

  • Single-crystal X-ray study
  • T = 290 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.027
  • wR factor = 0.062
  • Data-to-parameter ratio = 11.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

The crystal structure of the title compound, (I), was previously determined [Watson, 1960; CSD refcode BENBRN (Allen & Kennard, 1993); Gopalakrishna, 1969; CSD refcode BENBRN01], but the coordinates were never published. In addition, in the first case, the intensity data were partially measured on a single-crystal Geiger counter spectrometer, and partially determined by photographic techniques [R(0kl) = 0.097,and R(h0l) = 0.087]. In the second case, intensity data were measured using the stationary crystal–stationary counter technique (R = 0.12). Thus, now, we present the structure of (I), determined with significantly higher precision than the previous determinations.

A perspective view of (I) together with the atom-numbering scheme is shown in Fig. 1. A l l interatomic distances can be considered as normal. The benzene ring is very slightly distorted from planarity [the maximum deviation 0.016 (2) Å occurs for C2]. Atoms Br1, N1, N2 deviate, respectively, by -0.167 (3), 0.024 (4) and -0.103 (4) Å from weighted least-squares plane of the benzene ring. The weighted least-squares plane calculated through the atoms of the 2-nitro group make an angle of 42.3 (3)° with the above plane; it is caused by steric hindrance between the 2-nitro group and atom Br1. This also affects the position of the Br atom, which is shifted away from the 2-nitro group (Table 1). The weighted least-squares plane calculated through the atoms of the 4-nitro group makes an angle of 9.7 (3)° with the weighted least-squares plane of the benzene ring. This twist can by explained short by C—H···O intermolecular interactions (Table 2 and Fig. 2), which can be considered as weak intermolecular hydrogen bonds (Taylor & Kennard, 1982; Desiraju & Steiner, 1999). In this way, a one-dimensional hydrogen-bonded chain along z axis is created. In addition, in the structure, there are two more short contacts. These are caused by stacking interactions between the benzene rings: (i) symmetry transformation -x + 3/2, -y + 1/2, z; the distance between the ring centroids is 3.639 (3) Å, the perpendicular distance between the two benzene rings is 3.557 (3) Å and the angle between the two mentioned vectors is 12.2 (3)°; (ii) symmetry transformation -x + 1, -y + 1, -z: the distance between the ring centroids is 4.863 (3) Å, the perpendicular distance between the two benzene rings is 3.484 (3) Å and the angle between the two mentioned vectors is 44.2 (3)°. Via these interactions, the structure is expanded to the three-dimensional net.

Experimental top

31.2 ml of a 3:1 (v/v) mixture of 95% H2SO4 and 69% HNO3 was heated to 363 K, and added drop by drop to 3.2 ml of bromobenzene. The mixture was heated at 406 K for 5 min, then cooled and poured onto ice. The mixture was stirred and the solid filtered off under low pressure, washed with water, and dried in air. Crude 1-bromo-2,4-dinitrobenzene was recrystallized from chloroform. After three weeks, the crystals were grown (total yield 55.1%).

Computing details top

Data collection: CrysAlis CCD v. 1.163 (UNIL IC & Kuma 2000); cell refinement: CrysAlis RED v. 1.163 (UNIL IC & Kuma 2000); data reduction: CrysAlis RED v. 1.163 (UNIL IC & Kuma 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1990b) ORTEP-3 W v. 1.062 (Farrugia 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 1990).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Part of the molecular packing of the title compound, showing the intermolecular hydrogen bonds creating a one-dimensional hydrogen-bonded chain along the z axis and two types of stacking interactions. Hydrogen bonds are indicated by dashed lines.
1-Bromo-2,4-dinitrobenzene top
Crystal data top
C6H3BrN2O4Dx = 2.094 Mg m3
Mr = 247.01Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PccnCell parameters from 4181 reflections
a = 8.8740 (5) Åθ = 5–22°
b = 11.2257 (5) ŵ = 5.23 mm1
c = 15.7326 (8) ÅT = 290 K
V = 1567.23 (14) Å3Prism, light yellow
Z = 80.69 × 0.27 × 0.27 mm
F(000) = 960
Data collection top
Kuma KM4-CCD
diffractometer
1401 independent reflections
Radiation source: fine-focus sealed tube1395 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
ω scansθmax = 25.1°, θmin = 3.9°
Absorption correction: numerical
X-RED. Stoe & Cie (1999)
h = 1010
Tmin = 0.103, Tmax = 0.357k = 1313
16718 measured reflectionsl = 1818
Refinement top
Refinement on F2Secondary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: diffmap
R[F2 > 2σ(F2)] = 0.027H-atom parameters constrained
wR(F2) = 0.062 w = 1/[σ2(Fo2) + (0.0208P)2 + 1.5927P]
where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max < 0.001
1401 reflectionsΔρmax = 0.28 e Å3
119 parametersΔρmin = 0.43 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0092 (5)
Crystal data top
C6H3BrN2O4V = 1567.23 (14) Å3
Mr = 247.01Z = 8
Orthorhombic, PccnMo Kα radiation
a = 8.8740 (5) ŵ = 5.23 mm1
b = 11.2257 (5) ÅT = 290 K
c = 15.7326 (8) Å0.69 × 0.27 × 0.27 mm
Data collection top
Kuma KM4-CCD
diffractometer
1401 independent reflections
Absorption correction: numerical
X-RED. Stoe & Cie (1999)
1395 reflections with I > 2σ(I)
Tmin = 0.103, Tmax = 0.357Rint = 0.046
16718 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.062H-atom parameters constrained
S = 1.14Δρmax = 0.28 e Å3
1401 reflectionsΔρmin = 0.43 e Å3
119 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.

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
xyzUiso*/Ueq
Br10.23777 (4)0.95257 (3)0.075282 (17)0.05155 (16)
C10.1416 (3)0.8903 (2)0.02146 (14)0.0341 (5)
C20.1801 (3)0.9229 (2)0.10375 (15)0.0325 (5)
C30.1179 (3)0.8667 (2)0.17339 (14)0.0351 (5)
H30.14640.88710.22840.042*
C40.0121 (3)0.7796 (2)0.15854 (15)0.0328 (5)
C50.0326 (3)0.7481 (2)0.07770 (15)0.0360 (6)
H50.10660.69050.06960.043*
C60.0336 (3)0.8029 (2)0.00934 (15)0.0368 (6)
H60.00570.78140.04550.044*
N10.2928 (3)1.0162 (2)0.12129 (15)0.0408 (5)
O10.3823 (2)0.9961 (2)0.17805 (15)0.0612 (6)
O20.2866 (3)1.1074 (2)0.07997 (14)0.0606 (6)
N20.0497 (3)0.7141 (2)0.23176 (14)0.0417 (5)
O30.1528 (2)0.64384 (19)0.21890 (13)0.0558 (5)
O40.0069 (3)0.7323 (2)0.30029 (13)0.0654 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0703 (3)0.0495 (2)0.03485 (19)0.00846 (14)0.01487 (13)0.00251 (11)
C10.0392 (13)0.0349 (12)0.0281 (11)0.0065 (10)0.0055 (10)0.0026 (10)
C20.0318 (12)0.0306 (11)0.0351 (12)0.0016 (10)0.0013 (10)0.0035 (10)
C30.0412 (14)0.0379 (13)0.0264 (12)0.0074 (11)0.0032 (10)0.0029 (10)
C40.0354 (13)0.0344 (12)0.0285 (11)0.0065 (10)0.0038 (10)0.0034 (9)
C50.0369 (13)0.0351 (12)0.0361 (13)0.0014 (10)0.0031 (11)0.0008 (10)
C60.0448 (15)0.0395 (13)0.0262 (11)0.0007 (11)0.0032 (10)0.0030 (10)
N10.0403 (12)0.0374 (12)0.0446 (12)0.0002 (10)0.0022 (10)0.0063 (10)
O10.0525 (13)0.0503 (12)0.0807 (16)0.0008 (10)0.0275 (11)0.0051 (11)
O20.0799 (16)0.0439 (12)0.0579 (13)0.0171 (11)0.0060 (11)0.0055 (10)
N20.0473 (13)0.0423 (12)0.0357 (12)0.0099 (11)0.0093 (10)0.0049 (9)
O30.0519 (12)0.0567 (12)0.0590 (13)0.0056 (10)0.0132 (10)0.0122 (10)
O40.0946 (18)0.0714 (15)0.0302 (10)0.0042 (13)0.0019 (12)0.0077 (9)
Geometric parameters (Å, º) top
Br1—C11.880 (2)C4—N21.472 (3)
C1—C61.384 (3)C5—C61.372 (3)
C1—C21.388 (3)C5—H50.9300
C2—C31.379 (3)C6—H60.9300
C2—N11.474 (3)N1—O21.214 (3)
C3—C41.376 (4)N1—O11.216 (3)
C3—H30.9300N2—O41.207 (3)
C4—C51.379 (3)N2—O31.225 (3)
C6—C1—C2119.1 (2)C6—C5—C4119.0 (2)
C6—C1—Br1117.79 (17)C6—C5—H5120.5
C2—C1—Br1123.04 (19)C4—C5—H5120.5
C3—C2—C1121.4 (2)C5—C6—C1120.4 (2)
C3—C2—N1116.6 (2)C5—C6—H6119.8
C1—C2—N1121.9 (2)C1—C6—H6119.8
C4—C3—C2117.6 (2)O2—N1—O1125.4 (2)
C4—C3—H3121.2O2—N1—C2117.9 (2)
C2—C3—H3121.2O1—N1—C2116.6 (2)
C3—C4—C5122.4 (2)O4—N2—O3124.6 (2)
C3—C4—N2118.4 (2)O4—N2—C4117.3 (2)
C5—C4—N2119.1 (2)O3—N2—C4118.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O4i0.932.433.321 (3)160
Symmetry code: (i) x, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC6H3BrN2O4
Mr247.01
Crystal system, space groupOrthorhombic, Pccn
Temperature (K)290
a, b, c (Å)8.8740 (5), 11.2257 (5), 15.7326 (8)
V3)1567.23 (14)
Z8
Radiation typeMo Kα
µ (mm1)5.23
Crystal size (mm)0.69 × 0.27 × 0.27
Data collection
DiffractometerKuma KM4-CCD
diffractometer
Absorption correctionNumerical
X-RED. Stoe & Cie (1999)
Tmin, Tmax0.103, 0.357
No. of measured, independent and
observed [I > 2σ(I)] reflections
16718, 1401, 1395
Rint0.046
(sin θ/λ)max1)0.597
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.062, 1.14
No. of reflections1401
No. of parameters119
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.43

Computer programs: CrysAlis CCD v. 1.163 (UNIL IC & Kuma 2000), CrysAlis RED v. 1.163 (UNIL IC & Kuma 2000), SHELXS97 (Sheldrick, 1990a), XP in SHELXTL/PC (Sheldrick, 1990b) ORTEP-3 W v. 1.062 (Farrugia 1997), SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 1990).

Selected bond angles (º) top
C6—C1—C2119.1 (2)C4—C3—C2117.6 (2)
C6—C1—Br1117.79 (17)C3—C4—C5122.4 (2)
C2—C1—Br1123.04 (19)C3—C4—N2118.4 (2)
C3—C2—C1121.4 (2)C5—C4—N2119.1 (2)
C3—C2—N1116.6 (2)C6—C5—C4119.0 (2)
C1—C2—N1121.9 (2)C5—C6—C1120.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O4i0.932.433.321 (3)160.3
Symmetry code: (i) x, y+3/2, z+1/2.
 

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