4,6-Dinitro­benzene-1,3-diamine

Tian Zhou; De-Fu Han; Yong-Jun Hu

doi:10.1107/S1600536808009318

. 2008 Apr 16;64(Pt 5):o840. doi: 10.1107/S1600536808009318

4,6-Dinitrobenzene-1,3-diamine

Tian Zhou ^a,^*, De-Fu Han ^b, Yong-Jun Hu ^b

PMCID: PMC2961321 PMID: 21202328

Abstract

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.

Related literature

For related literature, see: Siri & Braunstein (2005 ▶).

Experimental

Crystal data

C₆H₆N₄O₄
M _r = 198.15
Triclinic,
a = 7.1294 (6) Å
b = 7.1770 (9) Å
c = 9.1289 (8) Å
α = 67.710 (6)°
β = 86.692 (6)°
γ = 62.214 (5)°
V = 378.30 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 295 (2) K
0.23 × 0.21 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.967, T _max = 0.972
2447 measured reflections
1322 independent reflections
1098 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.187
S = 1.00
1322 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808009318/hb2712sup1.cif

e-64-0o840-sup1.cif^{(13.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009318/hb2712Isup2.hkl

e-64-0o840-Isup2.hkl^{(65.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

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

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors acknowledge financial support from the Science Foundation of Maoming University (grant No. 208033).

supplementary crystallographic information

Comment

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).

Experimental

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%.