Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802005718/bt6132sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802005718/bt6132Isup2.hkl |
CCDC reference: 185768
Key indicators
- Single-crystal X-ray study
- T = 290 K
- Mean (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
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%).
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).
C6H3BrN2O4 | Dx = 2.094 Mg m−3 |
Mr = 247.01 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pccn | Cell parameters from 4181 reflections |
a = 8.8740 (5) Å | θ = 5–22° |
b = 11.2257 (5) Å | µ = 5.23 mm−1 |
c = 15.7326 (8) Å | T = 290 K |
V = 1567.23 (14) Å3 | Prism, light yellow |
Z = 8 | 0.69 × 0.27 × 0.27 mm |
F(000) = 960 |
Kuma KM4-CCD diffractometer | 1401 independent reflections |
Radiation source: fine-focus sealed tube | 1395 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ω scans | θmax = 25.1°, θmin = 3.9° |
Absorption correction: numerical X-RED. Stoe & Cie (1999) | h = −10→10 |
Tmin = 0.103, Tmax = 0.357 | k = −13→13 |
16718 measured reflections | l = −18→18 |
Refinement on F2 | Secondary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: diffmap |
R[F2 > 2σ(F2)] = 0.027 | H-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 reflections | Δρmax = 0.28 e Å−3 |
119 parameters | Δρmin = −0.43 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0092 (5) |
C6H3BrN2O4 | V = 1567.23 (14) Å3 |
Mr = 247.01 | Z = 8 |
Orthorhombic, Pccn | Mo Kα radiation |
a = 8.8740 (5) Å | µ = 5.23 mm−1 |
b = 11.2257 (5) Å | T = 290 K |
c = 15.7326 (8) Å | 0.69 × 0.27 × 0.27 mm |
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 = 0.357 | Rint = 0.046 |
16718 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.28 e Å−3 |
1401 reflections | Δρmin = −0.43 e Å−3 |
119 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.23777 (4) | 0.95257 (3) | 0.075282 (17) | 0.05155 (16) | |
C1 | 0.1416 (3) | 0.8903 (2) | −0.02146 (14) | 0.0341 (5) | |
C2 | 0.1801 (3) | 0.9229 (2) | −0.10375 (15) | 0.0325 (5) | |
C3 | 0.1179 (3) | 0.8667 (2) | −0.17339 (14) | 0.0351 (5) | |
H3 | 0.1464 | 0.8871 | −0.2284 | 0.042* | |
C4 | 0.0121 (3) | 0.7796 (2) | −0.15854 (15) | 0.0328 (5) | |
C5 | −0.0326 (3) | 0.7481 (2) | −0.07770 (15) | 0.0360 (6) | |
H5 | −0.1066 | 0.6905 | −0.0696 | 0.043* | |
C6 | 0.0336 (3) | 0.8029 (2) | −0.00934 (15) | 0.0368 (6) | |
H6 | 0.0057 | 0.7814 | 0.0455 | 0.044* | |
N1 | 0.2928 (3) | 1.0162 (2) | −0.12129 (15) | 0.0408 (5) | |
O1 | 0.3823 (2) | 0.9961 (2) | −0.17805 (15) | 0.0612 (6) | |
O2 | 0.2866 (3) | 1.1074 (2) | −0.07997 (14) | 0.0606 (6) | |
N2 | −0.0497 (3) | 0.7141 (2) | −0.23176 (14) | 0.0417 (5) | |
O3 | −0.1528 (2) | 0.64384 (19) | −0.21890 (13) | 0.0558 (5) | |
O4 | 0.0069 (3) | 0.7323 (2) | −0.30029 (13) | 0.0654 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0703 (3) | 0.0495 (2) | 0.03485 (19) | −0.00846 (14) | −0.01487 (13) | −0.00251 (11) |
C1 | 0.0392 (13) | 0.0349 (12) | 0.0281 (11) | 0.0065 (10) | −0.0055 (10) | −0.0026 (10) |
C2 | 0.0318 (12) | 0.0306 (11) | 0.0351 (12) | 0.0016 (10) | 0.0013 (10) | 0.0035 (10) |
C3 | 0.0412 (14) | 0.0379 (13) | 0.0264 (12) | 0.0074 (11) | 0.0032 (10) | 0.0029 (10) |
C4 | 0.0354 (13) | 0.0344 (12) | 0.0285 (11) | 0.0065 (10) | −0.0038 (10) | −0.0034 (9) |
C5 | 0.0369 (13) | 0.0351 (12) | 0.0361 (13) | −0.0014 (10) | 0.0031 (11) | 0.0008 (10) |
C6 | 0.0448 (15) | 0.0395 (13) | 0.0262 (11) | 0.0007 (11) | 0.0032 (10) | 0.0030 (10) |
N1 | 0.0403 (12) | 0.0374 (12) | 0.0446 (12) | 0.0002 (10) | 0.0022 (10) | 0.0063 (10) |
O1 | 0.0525 (13) | 0.0503 (12) | 0.0807 (16) | −0.0008 (10) | 0.0275 (11) | 0.0051 (11) |
O2 | 0.0799 (16) | 0.0439 (12) | 0.0579 (13) | −0.0171 (11) | 0.0060 (11) | −0.0055 (10) |
N2 | 0.0473 (13) | 0.0423 (12) | 0.0357 (12) | 0.0099 (11) | −0.0093 (10) | −0.0049 (9) |
O3 | 0.0519 (12) | 0.0567 (12) | 0.0590 (13) | −0.0056 (10) | −0.0132 (10) | −0.0122 (10) |
O4 | 0.0946 (18) | 0.0714 (15) | 0.0302 (10) | −0.0042 (13) | −0.0019 (12) | −0.0077 (9) |
Br1—C1 | 1.880 (2) | C4—N2 | 1.472 (3) |
C1—C6 | 1.384 (3) | C5—C6 | 1.372 (3) |
C1—C2 | 1.388 (3) | C5—H5 | 0.9300 |
C2—C3 | 1.379 (3) | C6—H6 | 0.9300 |
C2—N1 | 1.474 (3) | N1—O2 | 1.214 (3) |
C3—C4 | 1.376 (4) | N1—O1 | 1.216 (3) |
C3—H3 | 0.9300 | N2—O4 | 1.207 (3) |
C4—C5 | 1.379 (3) | N2—O3 | 1.225 (3) |
C6—C1—C2 | 119.1 (2) | C6—C5—C4 | 119.0 (2) |
C6—C1—Br1 | 117.79 (17) | C6—C5—H5 | 120.5 |
C2—C1—Br1 | 123.04 (19) | C4—C5—H5 | 120.5 |
C3—C2—C1 | 121.4 (2) | C5—C6—C1 | 120.4 (2) |
C3—C2—N1 | 116.6 (2) | C5—C6—H6 | 119.8 |
C1—C2—N1 | 121.9 (2) | C1—C6—H6 | 119.8 |
C4—C3—C2 | 117.6 (2) | O2—N1—O1 | 125.4 (2) |
C4—C3—H3 | 121.2 | O2—N1—C2 | 117.9 (2) |
C2—C3—H3 | 121.2 | O1—N1—C2 | 116.6 (2) |
C3—C4—C5 | 122.4 (2) | O4—N2—O3 | 124.6 (2) |
C3—C4—N2 | 118.4 (2) | O4—N2—C4 | 117.3 (2) |
C5—C4—N2 | 119.1 (2) | O3—N2—C4 | 118.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O4i | 0.93 | 2.43 | 3.321 (3) | 160 |
Symmetry code: (i) x, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C6H3BrN2O4 |
Mr | 247.01 |
Crystal system, space group | Orthorhombic, Pccn |
Temperature (K) | 290 |
a, b, c (Å) | 8.8740 (5), 11.2257 (5), 15.7326 (8) |
V (Å3) | 1567.23 (14) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 5.23 |
Crystal size (mm) | 0.69 × 0.27 × 0.27 |
Data collection | |
Diffractometer | Kuma KM4-CCD diffractometer |
Absorption correction | Numerical X-RED. Stoe & Cie (1999) |
Tmin, Tmax | 0.103, 0.357 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16718, 1401, 1395 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.062, 1.14 |
No. of reflections | 1401 |
No. of parameters | 119 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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).
C6—C1—C2 | 119.1 (2) | C4—C3—C2 | 117.6 (2) |
C6—C1—Br1 | 117.79 (17) | C3—C4—C5 | 122.4 (2) |
C2—C1—Br1 | 123.04 (19) | C3—C4—N2 | 118.4 (2) |
C3—C2—C1 | 121.4 (2) | C5—C4—N2 | 119.1 (2) |
C3—C2—N1 | 116.6 (2) | C6—C5—C4 | 119.0 (2) |
C1—C2—N1 | 121.9 (2) | C5—C6—C1 | 120.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O4i | 0.93 | 2.43 | 3.321 (3) | 160.3 |
Symmetry code: (i) x, −y+3/2, z+1/2. |
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.