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Acta Cryst. (2008). E64, o840    [ doi:10.1107/S1600536808009318 ]

4,6-Dinitrobenzene-1,3-diamine

T. Zhou, D.-F. Han and Y.-J. Hu

Abstract top

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.

Comment top

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).

Related literature top

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

Experimental top

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%.

Refinement top

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).

Computing details top

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

Figures top
[Figure 1] 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.
4,6-Dinitrobenzene-1,3-diamine top
Crystal data top
C6H6N4O4Z = 2
Mr = 198.15F(000) = 204
Triclinic, P1Dx = 1.740 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.1294 (6) ÅCell parameters from 1322 reflections
b = 7.1770 (9) Åθ = 3.4–25.1°
c = 9.1289 (8) ŵ = 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
Data collection top
Bruker APEXII CCD
diffractometer		1322 independent reflections
Radiation source: fine-focus sealed tube1098 reflections with I > 2σ(I)
graphiteRint = 0.024
φ and ω scansθmax = 25.1°, θmin = 3.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −8→8
Tmin = 0.967, Tmax = 0.972k = −3→8
2447 measured reflectionsl = −9→10
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.187H-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 parametersΔρmax = 0.50 e Å−3
0 restraintsΔρmin = −0.24 e Å−3
Crystal data top
C6H6N4O4γ = 62.214 (5)°
Mr = 198.15V = 378.30 (7) Å3
Triclinic, P1Z = 2
a = 7.1294 (6) ÅMo Kα radiation
b = 7.1770 (9) ŵ = 0.15 mm−1
c = 9.1289 (8) ÅT = 295 K
α = 67.710 (6)°0.23 × 0.21 × 0.19 mm
β = 86.692 (6)°
Data collection top
Bruker APEXII CCD
diffractometer		1322 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		1098 reflections with I > 2σ(I)
Tmin = 0.967, Tmax = 0.972Rint = 0.024
2447 measured reflectionsθmax = 25.1°
Refinement top
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.187Δρmax = 0.50 e Å−3
S = 1.00Δρmin = −0.24 e Å−3
1322 reflectionsAbsolute structure: ?
127 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
C10.2508 (3)0.6981 (4)0.8212 (2)0.0307 (5)
C20.2639 (3)0.8653 (4)0.6845 (2)0.0325 (6)
H20.27230.98440.69650.039*
C30.2654 (3)0.8654 (3)0.5319 (2)0.0291 (5)
C40.2464 (3)0.6832 (3)0.5162 (2)0.0284 (5)
C50.2400 (3)0.5121 (3)0.6491 (2)0.0308 (5)
H50.23170.39320.63690.037*
C60.2457 (3)0.5127 (3)0.7994 (2)0.0312 (5)
N10.2441 (3)0.7171 (3)0.9615 (2)0.0399 (6)
H1A0.24780.83190.96780.048*
H1B0.23600.61461.04550.048*
N20.2856 (3)1.0298 (3)0.4091 (2)0.0397 (5)
H2A0.29771.13470.42480.048*
H2B0.28651.03000.31480.048*
N30.2326 (3)0.6701 (3)0.3643 (2)0.0332 (5)
N40.2487 (3)0.3197 (3)0.9290 (2)0.0390 (5)
O10.2415 (3)0.8172 (3)0.24312 (17)0.0490 (5)
O20.2106 (3)0.5129 (3)0.35769 (19)0.0501 (5)
O30.2537 (4)0.1638 (3)0.9013 (2)0.0635 (7)
O40.2458 (3)0.3152 (3)1.06588 (18)0.0539 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0380 (11)0.0317 (11)0.0225 (10)−0.0169 (9)0.0053 (8)−0.0108 (8)
C20.0471 (12)0.0284 (11)0.0280 (12)−0.0218 (9)0.0058 (9)−0.0126 (9)
C30.0360 (11)0.0269 (11)0.0236 (10)−0.0160 (8)0.0051 (8)−0.0082 (8)
C40.0354 (11)0.0300 (11)0.0207 (10)−0.0149 (9)0.0052 (7)−0.0122 (9)
C50.0401 (11)0.0256 (10)0.0287 (11)−0.0172 (9)0.0043 (8)−0.0112 (9)
C60.0415 (11)0.0288 (11)0.0220 (11)−0.0186 (9)0.0041 (8)−0.0065 (9)
N10.0684 (13)0.0374 (11)0.0218 (10)−0.0307 (10)0.0093 (8)−0.0132 (8)
N20.0674 (13)0.0363 (10)0.0241 (9)−0.0343 (10)0.0092 (8)−0.0091 (8)
N30.0443 (10)0.0319 (10)0.0253 (9)−0.0185 (8)0.0041 (7)−0.0129 (8)
N40.0593 (12)0.0337 (11)0.0265 (9)−0.0268 (9)0.0078 (8)−0.0090 (8)
O10.0861 (13)0.0490 (11)0.0202 (8)−0.0406 (9)0.0121 (7)−0.0121 (8)
O20.0847 (12)0.0457 (10)0.0358 (10)−0.0388 (9)0.0054 (8)−0.0217 (8)
O30.1255 (18)0.0439 (11)0.0397 (10)−0.0569 (12)0.0171 (10)−0.0147 (9)
O40.0979 (14)0.0498 (11)0.0214 (9)−0.0460 (10)0.0134 (8)−0.0087 (8)
Geometric parameters (Å, °) top
C1—N11.334 (3)C5—H50.9300
C1—C21.401 (3)C6—N41.432 (3)
C1—C61.435 (3)N1—H1A0.8600
C2—C31.392 (3)N1—H1B0.8600
C2—H20.9300N2—H2A0.8600
C3—N21.344 (3)N2—H2B0.8600
C3—C41.434 (3)N3—O11.229 (2)
C4—C51.377 (3)N3—O21.233 (2)
C4—N31.437 (3)N4—O31.222 (3)
C5—C61.377 (3)N4—O41.236 (3)
N1—C1—C2119.87 (19)C5—C6—N4116.47 (18)
N1—C1—C6123.84 (19)C5—C6—C1120.45 (19)
C2—C1—C6116.29 (19)N4—C6—C1123.07 (19)
C3—C2—C1124.43 (19)C1—N1—H1A120.0
C3—C2—H2117.8C1—N1—H1B120.0
C1—C2—H2117.8H1A—N1—H1B120.0
N2—C3—C2119.92 (18)C3—N2—H2A120.0
N2—C3—C4123.51 (19)C3—N2—H2B120.0
C2—C3—C4116.57 (18)H2A—N2—H2B120.0
C5—C4—C3120.39 (19)O1—N3—O2121.21 (18)
C5—C4—N3117.18 (18)O1—N3—C4119.26 (17)
C3—C4—N3122.43 (19)O2—N3—C4119.52 (17)
C4—C5—C6121.69 (19)O3—N4—O4121.72 (17)
C4—C5—H5119.2O3—N4—C6119.01 (18)
C6—C5—H5119.2O4—N4—C6119.27 (18)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.862.243.074 (2)162
N1—H1A···O1ii0.862.472.917 (2)113
N1—H1B···O40.862.052.667 (3)128
N2—H2A···O2i0.862.313.098 (2)152
N2—H2B···O10.862.032.642 (2)128
N2—H2B···O4iii0.862.332.964 (3)131
Symmetry codes: (i) x, y+1, z; (ii) x, y, z+1; (iii) x, y+1, z−1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.862.243.074 (2)162
N1—H1A···O1ii0.862.472.917 (2)113
N1—H1B···O40.862.052.667 (3)128
N2—H2A···O2i0.862.313.098 (2)152
N2—H2B···O10.862.032.642 (2)128
N2—H2B···O4iii0.862.332.964 (3)131
Symmetry codes: (i) x, y+1, z; (ii) x, y, z+1; (iii) x, y+1, z−1.
references
References top

Bruker (2001). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2004). SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Siri, O. & Braunstein, P. (2005). New J. Chem. 29, 75–78.