4,6-Dinitro­benzene-1,3-diamine

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

doi:10.1107/S1600536808009318

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o840

doi:10.1107/S1600536808009318

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4,6-Dinitrobenzene-1,3-diamine

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

^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

(Received 27 March 2008; accepted 6 April 2008; online 16 April 2008)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.051
wR(F²) = 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

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
Symmetry codes: (i) x, y+1, z; (ii) x, y, z+1; (iii) x, y+1, z-1.

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.

Supporting information

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

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

checkCIF report

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%.

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

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

C₆H₆N₄O₄	Z = 2
M_r = 198.15	F(000) = 204
Triclinic, P1	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	1322 independent reflections
Radiation source: fine-focus sealed tube	1098 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 25.1°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→8
T_min = 0.967, T_max = 0.972	k = −3→8
2447 measured reflections	l = −9→10

Refinement top

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(F_o²) + (0.15P)² + 0.0584P] where P = (F_o² + 2F_c²)/3
1322 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₆H₆N₄O₄	γ = 62.214 (5)°
M_r = 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)°

Data collection top

Bruker APEXII CCD diffractometer	1322 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1098 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.972	R_int = 0.024
2447 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.187	H-atom parameters constrained
S = 1.00	Δρ_max = 0.50 e Å⁻³
1322 reflections	Δρ_min = −0.24 e Å⁻³
127 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

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.967, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	2447, 1322, 1098
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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

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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