organic compounds
4,6-Dinitrobenzene-1,3-diamine
aSchool of Chemistry and Life Science, Maoming University, Maoming 525000, People's Republic of China, and bSchool of Life Science, Changchun Normal University, Changchun 130032, People's Republic of China
*Correspondence e-mail: zhout016@nenu.edu.cn
The molecule of the title compound, C6H6N4O4, is almost planar, being stabilized by two intramolecular N—H⋯O hydrogen bonds. Further N—H⋯O links lead to a sheet in the crystal structure.
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536808009318/hb2712sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808009318/hb2712Isup2.hkl
80 ml concentrated HN03 was added dropwise to 29.2 g 1,3-dichlorobenzene in 150 ml oleum (25% sulfur trioxide) and the mixture was stirred for 30 minutes. The resulting solution was poured over 2000 g crushed ice. After the ice has melted, sufficient 30% sodium hydroxide solution was added to achieve a pH of 7 and 24.2 g of 1,3-dinitro-4,6-dichlorobenzene (II) was obtained after filtration and drying. Then, 7.2 g of (II) and 50 ml 30% aqueous ammonia were sealed in a 100-ml autoclave and heated to 443 K for 24 h. After cooling to room temperature, 5.6 g (23% yield) of colourless blocks of (I) were recovered. Anal. Calc. for C6H6N4O4: C 36.34, H 3.03, N 28.28%; Found: C 36.32, H 3.01, N 28.29%.
The H atoms were placed in calculated positions with C—H = 0.93Å and N—H = 0.86Å and refined as riding with Uiso(H) = 1.2Ueq(carrier).
Data collection: APEX2 (Bruker, 2004); cell
SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of (I), drawn with 50% displacement ellipsoids for the non-hydrogen atoms. The hydrogen bonds are shown as double-dashed lines. |
C6H6N4O4 | Z = 2 |
Mr = 198.15 | F(000) = 204 |
Triclinic, P1 | Dx = 1.740 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1294 (6) Å | Cell parameters from 1322 reflections |
b = 7.1770 (9) Å | θ = 3.4–25.1° |
c = 9.1289 (8) Å | µ = 0.15 mm−1 |
α = 67.710 (6)° | T = 295 K |
β = 86.692 (6)° | Block, colourless |
γ = 62.214 (5)° | 0.23 × 0.21 × 0.19 mm |
V = 378.30 (7) Å3 |
Bruker APEXII CCD diffractometer | 1322 independent reflections |
Radiation source: fine-focus sealed tube | 1098 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ϕ and ω scans | θmax = 25.1°, θmin = 3.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −8→8 |
Tmin = 0.967, Tmax = 0.972 | k = −3→8 |
2447 measured reflections | l = −9→10 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.187 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.15P)2 + 0.0584P] where P = (Fo2 + 2Fc2)/3 |
1322 reflections | (Δ/σ)max < 0.001 |
127 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C6H6N4O4 | γ = 62.214 (5)° |
Mr = 198.15 | V = 378.30 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.1294 (6) Å | Mo Kα radiation |
b = 7.1770 (9) Å | µ = 0.15 mm−1 |
c = 9.1289 (8) Å | T = 295 K |
α = 67.710 (6)° | 0.23 × 0.21 × 0.19 mm |
β = 86.692 (6)° |
Bruker APEXII CCD diffractometer | 1322 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1098 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.972 | Rint = 0.024 |
2447 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.187 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.50 e Å−3 |
1322 reflections | Δρmin = −0.24 e Å−3 |
127 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 | ||
C1 | 0.2508 (3) | 0.6981 (4) | 0.8212 (2) | 0.0307 (5) | |
C2 | 0.2639 (3) | 0.8653 (4) | 0.6845 (2) | 0.0325 (6) | |
H2 | 0.2723 | 0.9844 | 0.6965 | 0.039* | |
C3 | 0.2654 (3) | 0.8654 (3) | 0.5319 (2) | 0.0291 (5) | |
C4 | 0.2464 (3) | 0.6832 (3) | 0.5162 (2) | 0.0284 (5) | |
C5 | 0.2400 (3) | 0.5121 (3) | 0.6491 (2) | 0.0308 (5) | |
H5 | 0.2317 | 0.3932 | 0.6369 | 0.037* | |
C6 | 0.2457 (3) | 0.5127 (3) | 0.7994 (2) | 0.0312 (5) | |
N1 | 0.2441 (3) | 0.7171 (3) | 0.9615 (2) | 0.0399 (6) | |
H1A | 0.2478 | 0.8319 | 0.9678 | 0.048* | |
H1B | 0.2360 | 0.6146 | 1.0455 | 0.048* | |
N2 | 0.2856 (3) | 1.0298 (3) | 0.4091 (2) | 0.0397 (5) | |
H2A | 0.2977 | 1.1347 | 0.4248 | 0.048* | |
H2B | 0.2865 | 1.0300 | 0.3148 | 0.048* | |
N3 | 0.2326 (3) | 0.6701 (3) | 0.3643 (2) | 0.0332 (5) | |
N4 | 0.2487 (3) | 0.3197 (3) | 0.9290 (2) | 0.0390 (5) | |
O1 | 0.2415 (3) | 0.8172 (3) | 0.24312 (17) | 0.0490 (5) | |
O2 | 0.2106 (3) | 0.5129 (3) | 0.35769 (19) | 0.0501 (5) | |
O3 | 0.2537 (4) | 0.1638 (3) | 0.9013 (2) | 0.0635 (7) | |
O4 | 0.2458 (3) | 0.3152 (3) | 1.06588 (18) | 0.0539 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0380 (11) | 0.0317 (11) | 0.0225 (10) | −0.0169 (9) | 0.0053 (8) | −0.0108 (8) |
C2 | 0.0471 (12) | 0.0284 (11) | 0.0280 (12) | −0.0218 (9) | 0.0058 (9) | −0.0126 (9) |
C3 | 0.0360 (11) | 0.0269 (11) | 0.0236 (10) | −0.0160 (8) | 0.0051 (8) | −0.0082 (8) |
C4 | 0.0354 (11) | 0.0300 (11) | 0.0207 (10) | −0.0149 (9) | 0.0052 (7) | −0.0122 (9) |
C5 | 0.0401 (11) | 0.0256 (10) | 0.0287 (11) | −0.0172 (9) | 0.0043 (8) | −0.0112 (9) |
C6 | 0.0415 (11) | 0.0288 (11) | 0.0220 (11) | −0.0186 (9) | 0.0041 (8) | −0.0065 (9) |
N1 | 0.0684 (13) | 0.0374 (11) | 0.0218 (10) | −0.0307 (10) | 0.0093 (8) | −0.0132 (8) |
N2 | 0.0674 (13) | 0.0363 (10) | 0.0241 (9) | −0.0343 (10) | 0.0092 (8) | −0.0091 (8) |
N3 | 0.0443 (10) | 0.0319 (10) | 0.0253 (9) | −0.0185 (8) | 0.0041 (7) | −0.0129 (8) |
N4 | 0.0593 (12) | 0.0337 (11) | 0.0265 (9) | −0.0268 (9) | 0.0078 (8) | −0.0090 (8) |
O1 | 0.0861 (13) | 0.0490 (11) | 0.0202 (8) | −0.0406 (9) | 0.0121 (7) | −0.0121 (8) |
O2 | 0.0847 (12) | 0.0457 (10) | 0.0358 (10) | −0.0388 (9) | 0.0054 (8) | −0.0217 (8) |
O3 | 0.1255 (18) | 0.0439 (11) | 0.0397 (10) | −0.0569 (12) | 0.0171 (10) | −0.0147 (9) |
O4 | 0.0979 (14) | 0.0498 (11) | 0.0214 (9) | −0.0460 (10) | 0.0134 (8) | −0.0087 (8) |
C1—N1 | 1.334 (3) | C5—H5 | 0.9300 |
C1—C2 | 1.401 (3) | C6—N4 | 1.432 (3) |
C1—C6 | 1.435 (3) | N1—H1A | 0.8600 |
C2—C3 | 1.392 (3) | N1—H1B | 0.8600 |
C2—H2 | 0.9300 | N2—H2A | 0.8600 |
C3—N2 | 1.344 (3) | N2—H2B | 0.8600 |
C3—C4 | 1.434 (3) | N3—O1 | 1.229 (2) |
C4—C5 | 1.377 (3) | N3—O2 | 1.233 (2) |
C4—N3 | 1.437 (3) | N4—O3 | 1.222 (3) |
C5—C6 | 1.377 (3) | N4—O4 | 1.236 (3) |
N1—C1—C2 | 119.87 (19) | C5—C6—N4 | 116.47 (18) |
N1—C1—C6 | 123.84 (19) | C5—C6—C1 | 120.45 (19) |
C2—C1—C6 | 116.29 (19) | N4—C6—C1 | 123.07 (19) |
C3—C2—C1 | 124.43 (19) | C1—N1—H1A | 120.0 |
C3—C2—H2 | 117.8 | C1—N1—H1B | 120.0 |
C1—C2—H2 | 117.8 | H1A—N1—H1B | 120.0 |
N2—C3—C2 | 119.92 (18) | C3—N2—H2A | 120.0 |
N2—C3—C4 | 123.51 (19) | C3—N2—H2B | 120.0 |
C2—C3—C4 | 116.57 (18) | H2A—N2—H2B | 120.0 |
C5—C4—C3 | 120.39 (19) | O1—N3—O2 | 121.21 (18) |
C5—C4—N3 | 117.18 (18) | O1—N3—C4 | 119.26 (17) |
C3—C4—N3 | 122.43 (19) | O2—N3—C4 | 119.52 (17) |
C4—C5—C6 | 121.69 (19) | O3—N4—O4 | 121.72 (17) |
C4—C5—H5 | 119.2 | O3—N4—C6 | 119.01 (18) |
C6—C5—H5 | 119.2 | O4—N4—C6 | 119.27 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3i | 0.86 | 2.24 | 3.074 (2) | 162 |
N1—H1A···O1ii | 0.86 | 2.47 | 2.917 (2) | 113 |
N1—H1B···O4 | 0.86 | 2.05 | 2.667 (3) | 128 |
N2—H2A···O2i | 0.86 | 2.31 | 3.098 (2) | 152 |
N2—H2B···O1 | 0.86 | 2.03 | 2.642 (2) | 128 |
N2—H2B···O4iii | 0.86 | 2.33 | 2.964 (3) | 131 |
Symmetry codes: (i) x, y+1, z; (ii) x, y, z+1; (iii) x, y+1, z−1. |
Experimental details
Crystal data | |
Chemical formula | C6H6N4O4 |
Mr | 198.15 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 7.1294 (6), 7.1770 (9), 9.1289 (8) |
α, β, γ (°) | 67.710 (6), 86.692 (6), 62.214 (5) |
V (Å3) | 378.30 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.15 |
Crystal size (mm) | 0.23 × 0.21 × 0.19 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.967, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2447, 1322, 1098 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.187, 1.00 |
No. of reflections | 1322 |
No. of parameters | 127 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.24 |
Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3i | 0.86 | 2.24 | 3.074 (2) | 162 |
N1—H1A···O1ii | 0.86 | 2.47 | 2.917 (2) | 113 |
N1—H1B···O4 | 0.86 | 2.05 | 2.667 (3) | 128 |
N2—H2A···O2i | 0.86 | 2.31 | 3.098 (2) | 152 |
N2—H2B···O1 | 0.86 | 2.03 | 2.642 (2) | 128 |
N2—H2B···O4iii | 0.86 | 2.33 | 2.964 (3) | 131 |
Symmetry codes: (i) x, y+1, z; (ii) x, y, z+1; (iii) x, y+1, z−1. |
Acknowledgements
The authors acknowledge financial support from the Science Foundation of Maoming University (grant No. 208033).
References
Bruker (2001). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siri, O. & Braunstein, P. (2005). New J. Chem. 29, 75–78. Web of Science CSD CrossRef CAS Google Scholar
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As part of the ongoing investigations of biological structure-property relationships in amino-containing molecules (Siri & Braunstein, 2005), we now report the synthesis and structure of the title compound, (I), (Fig. 1).
The molecule of (I) is almost planar, being stabilised by two intramolecular N-H···O interactions (Table 1). The aromatic ring makes dihedral angles of 3.7 (2)° and 4.6 (3)° with the N3/O1/O2 and N4/O3/O4 nitro groups, respectively. Further intermolecular N-H···O hydrogen bonds result in (100) sheets in the crystal (Fig. 2).