3-Nitro­benzene-1,2-diamine

Betz, R.; Gerber, T.

doi:10.1107/S1600536811016825

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1359

doi:10.1107/S1600536811016825

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3-Nitrobenzene-1,2-diamine

Richard Betz ^a ^* and Thomas Gerber ^a

^aNelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth 6031, South Africa
^*Correspondence e-mail: richard.betz@webmail.co.za

(Received 28 April 2011; accepted 4 May 2011; online 7 May 2011)

The molecule of the title compound, C₆H₇N₃O₂, a derivative of o-phenylenediamine, nearly shows non-crystallographic C_s symmetry. C—C—C angles span the range 116.25 (11)–122.35 (11)°. In the crystal, intermolecular N—H⋯O and N—H⋯N hydrogen bonds connect molecules into undulating sheets perpendicular to the crystallographic a axis. A weak intramolecular N—H⋯O hydrogen bond is also observed. No π-stacking is observed in the crystal structure.

Related literature

For the crystal structure of 1,2-diaminobenzene, see: Stalhandske (1981 ); Czapik & Gdaniec (2010 ). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ); Bernstein et al. (1995 ). For the use of chelate ligands in coordination chemistry, see: Gade (1998 ). For the crystal structures of coordination compounds with rhenium in different oxidation states applying (mixed) oxygen-, nitrogen- and/or sulfur-containing ligands, see: Chiozzone et al. (1999 ); Videira et al. (2009 ); Edwards et al. (1998 ); Marti et al. (2005 ); Babich et al. (2001 ).

Experimental

Crystal data

C₆H₇N₃O₂
M_r = 153.15
Monoclinic, P 2₁ /c
a = 13.2854 (5) Å
b = 3.7504 (1) Å
c = 16.3309 (6) Å
β = 126.208 (2)°
V = 656.55 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 200 K
0.55 × 0.24 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
6477 measured reflections
1605 independent reflections
1262 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.115
S = 1.05
1605 reflections
113 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H711⋯O1ⁱ	0.89 (1)	2.41 (2)	3.1257 (14)	138 (2)
N2—H721⋯N1ⁱⁱ	0.88 (1)	2.26 (1)	3.0800 (16)	156 (2)
N2—H722⋯O1	0.88 (1)	1.98 (1)	2.6084 (14)	127 (1)
N2—H722⋯O1ⁱⁱⁱ	0.88 (1)	2.55 (2)	3.1416 (16)	126 (1)
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z.

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811016825/sj5135sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811016825/sj5135Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811016825/sj5135Isup3.cml

checkCIF report

Comment top

Chelate ligands have found widespread use in coordination chemistry due to the enhanced thermodynamic stability of resultant coordination compounds in relation to coordination compounds exclusively applying comparable monodentate ligands (Gade 1998). Combining different sets of donor atoms in one chelate ligand molecule, a probe for testing and accomodating metal centers of different Lewis acidities is at hand. For the crystal structures of coordination compounds with rhenium in different oxidation states applying (mixed) oxygen-, nitrogen- and/or sulfur-containing ligands, see: Chiozzone et al. (1999); Videira et al. (2009); Edwards et al. (1998); Marti et al. (2005); Babich et al. (2001). The title compound, which offers two amino and one nitro group in close proximity to each other, seemed particularily interesting in this aspect. To enable comparative studies with the crystal structures of envisioned coordination compounds, the structure of the free ligand was determined. The crystal structure of 1,2-diaminobenzene is apparent in the literature (Stalhandske 1981, Czapik & Gdaniec 2010).

Intracyclic angles cover a range of 116–122 ° with the smallest angle present on the C-atom in between the C-atoms bearing the nitro as well as an amino group. The nitro group is nearly completely in plane with the aromatic system. The least-squares planes defined by their respective atoms intersect at an angle of only 3.93 (18) ° (Fig. 1).

Except for one of the H-atoms of the amino group in meta-position to the nitro group, all of the hydrogen atoms of the amino groups participate in hydrogen bonds in the crystal structure. While one of the O-atoms of the nitro group acts as twofold acceptor, the second one does not take part in this type of intermolecular contacts. In terms of graph-set analysis, (Etter et al. 1990, Bernstein et al. 1995), the descriptor for the hydrogen bonding system on the unitary level is C¹₁(5)C¹₁(7)R²₂(12). In total, the molecules are connected to waved sheets perpendicular to the crystallographic a-axis. π-stacking is not observed in the crystal structure of the title compound (Fig. 2).

The molecular packing is shown in Figure 3.

Related literature top

For the crystal structure of 1,2-diaminobenzene, see: Stalhandske (1981); Czapik & Gdaniec (2010). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990); Bernstein et al. (1995). For the use of chelate ligands in coordination chemistry, see: Gade (1998). For the crystal structures of coordination compounds with rhenium in different oxidation states applying (mixed) oxygen-, nitrogen- and/or sulfur-containing ligands, see: Chiozzone et al. (1999); Videira et al. (2009); Edwards et al. (1998); Marti et al. (2005); Babich et al. (2001).

Experimental top

The compound was obtained commercially (Aldrich). Crystals suitable for the X-ray diffraction study were obtained upon recrystallization from ethanol.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level).
	Fig. 2. Intermolecular contacts, viewed approximately along [010]. Symmetry operators: ⁱ x, -y + 3/2, z + 1/2; ⁱⁱ -x, y + 1/2, -z + 1/2; ⁱⁱⁱ -x, y - 1/2, -z + 1/2; ^iv -x, -y + 1, -z; ^v x, -y + 3/2, z - 1/2.
	Fig. 3. Molecular packing of the title compound, viewed along [0 1 0] (anisotropic displacement ellipsoids drawn at 50% probability level).

3-Nitrobenzene-1,2-diamine top

Crystal data top

C₆H₇N₃O₂	F(000) = 320
M_r = 153.15	D_x = 1.549 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3115 reflections
a = 13.2854 (5) Å	θ = 2.5–28.2°
b = 3.7504 (1) Å	µ = 0.12 mm⁻¹
c = 16.3309 (6) Å	T = 200 K
β = 126.208 (2)°	Rod, red
V = 656.55 (4) Å³	0.55 × 0.24 × 0.11 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1262 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.043
Graphite monochromator	θ_max = 28.3°, θ_min = 3.1°
ϕ and ω scans	h = −17→17
6477 measured reflections	k = −4→4
1605 independent reflections	l = −21→21

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.055P)² + 0.1822P] where P = (F_o² + 2F_c²)/3
1605 reflections	(Δ/σ)_max < 0.001
113 parameters	Δρ_max = 0.30 e Å⁻³
6 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₆H₇N₃O₂	V = 656.55 (4) Å³
M_r = 153.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.2854 (5) Å	µ = 0.12 mm⁻¹
b = 3.7504 (1) Å	T = 200 K
c = 16.3309 (6) Å	0.55 × 0.24 × 0.11 mm
β = 126.208 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1262 reflections with I > 2σ(I)
6477 measured reflections	R_int = 0.043
1605 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	6 restraints
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.30 e Å⁻³
1605 reflections	Δρ_min = −0.17 e Å⁻³
113 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.13915 (10)	0.7321 (4)	0.03335 (7)	0.0524 (3)
O2	0.30745 (12)	1.0010 (4)	0.07783 (10)	0.0687 (4)
N1	0.13706 (12)	0.8731 (4)	0.34249 (9)	0.0419 (3)
H711	0.1778 (16)	0.888 (5)	0.4092 (10)	0.063*
H712	0.1066 (16)	0.649 (4)	0.3250 (14)	0.063*
N2	0.07013 (10)	0.7189 (3)	0.15331 (8)	0.0346 (3)
H721	0.0209 (14)	0.662 (5)	0.1708 (12)	0.052*
H722	0.0458 (15)	0.663 (5)	0.0919 (10)	0.052*
N3	0.23536 (11)	0.9000 (3)	0.09715 (8)	0.0382 (3)
C1	0.22068 (11)	0.9559 (3)	0.31843 (9)	0.0289 (3)
C2	0.18152 (10)	0.8773 (3)	0.21809 (8)	0.0241 (3)
C3	0.26459 (10)	0.9743 (3)	0.19499 (8)	0.0268 (3)
C4	0.37907 (11)	1.1429 (3)	0.26574 (11)	0.0349 (3)
H4	0.4329	1.2060	0.2477	0.042*
C5	0.41227 (12)	1.2152 (4)	0.36057 (10)	0.0397 (3)
H5	0.4895	1.3289	0.4091	0.048*
C6	0.33235 (12)	1.1214 (4)	0.38622 (9)	0.0374 (3)
H6	0.3561	1.1739	0.4524	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0500 (6)	0.0787 (8)	0.0285 (5)	−0.0038 (6)	0.0231 (5)	−0.0108 (5)
O2	0.0701 (8)	0.1063 (11)	0.0630 (7)	−0.0052 (7)	0.0575 (7)	0.0026 (7)
N1	0.0512 (7)	0.0525 (8)	0.0371 (6)	0.0146 (6)	0.0344 (6)	0.0103 (6)
N2	0.0294 (5)	0.0433 (7)	0.0331 (5)	−0.0028 (4)	0.0195 (5)	−0.0030 (5)
N3	0.0430 (6)	0.0493 (7)	0.0343 (6)	0.0089 (5)	0.0294 (5)	0.0054 (5)
C1	0.0353 (6)	0.0286 (6)	0.0263 (5)	0.0121 (5)	0.0201 (5)	0.0066 (5)
C2	0.0261 (5)	0.0237 (5)	0.0244 (5)	0.0061 (4)	0.0160 (4)	0.0031 (4)
C3	0.0299 (6)	0.0276 (6)	0.0264 (5)	0.0052 (4)	0.0185 (5)	0.0035 (4)
C4	0.0300 (6)	0.0283 (6)	0.0472 (7)	0.0024 (5)	0.0233 (6)	0.0037 (5)
C5	0.0305 (6)	0.0294 (7)	0.0404 (7)	0.0011 (5)	0.0106 (5)	−0.0050 (5)
C6	0.0433 (7)	0.0331 (7)	0.0249 (6)	0.0114 (5)	0.0140 (5)	−0.0011 (5)

Geometric parameters (Å, º) top

O1—N3	1.2420 (16)	C1—C6	1.3681 (18)
O2—N3	1.2318 (15)	C1—C2	1.4268 (15)
N1—C1	1.4142 (16)	C2—C3	1.4088 (15)
N1—H711	0.887 (12)	C3—C4	1.4041 (17)
N1—H712	0.903 (12)	C4—C5	1.364 (2)
N2—C2	1.3462 (15)	C4—H4	0.9500
N2—H721	0.880 (12)	C5—C6	1.397 (2)
N2—H722	0.878 (12)	C5—H5	0.9500
N3—C3	1.4313 (15)	C6—H6	0.9500

C1—N1—H711	108.5 (12)	C3—C2—C1	116.25 (11)
C1—N1—H712	113.3 (12)	C4—C3—C2	122.35 (11)
H711—N1—H712	106.4 (15)	C4—C3—N3	117.01 (11)
C2—N2—H721	122.3 (11)	C2—C3—N3	120.64 (11)
C2—N2—H722	119.6 (11)	C5—C4—C3	119.38 (12)
H721—N2—H722	118.0 (14)	C5—C4—H4	120.3
O2—N3—O1	120.77 (12)	C3—C4—H4	120.3
O2—N3—C3	119.13 (12)	C4—C5—C6	119.81 (12)
O1—N3—C3	120.09 (10)	C4—C5—H5	120.1
C6—C1—N1	121.95 (11)	C6—C5—H5	120.1
C6—C1—C2	120.56 (11)	C1—C6—C5	121.65 (12)
N1—C1—C2	117.41 (11)	C1—C6—H6	119.2
N2—C2—C3	125.10 (10)	C5—C6—H6	119.2
N2—C2—C1	118.65 (10)

C6—C1—C2—N2	−179.04 (11)	O1—N3—C3—C4	175.60 (12)
N1—C1—C2—N2	−2.26 (17)	O2—N3—C3—C2	177.07 (12)
C6—C1—C2—C3	0.96 (17)	O1—N3—C3—C2	−3.77 (19)
N1—C1—C2—C3	177.74 (10)	C2—C3—C4—C5	0.29 (19)
N2—C2—C3—C4	179.27 (11)	N3—C3—C4—C5	−179.07 (11)
C1—C2—C3—C4	−0.73 (17)	C3—C4—C5—C6	−0.04 (19)
N2—C2—C3—N3	−1.39 (19)	N1—C1—C6—C5	−177.40 (12)
C1—C2—C3—N3	178.60 (10)	C2—C1—C6—C5	−0.78 (19)
O2—N3—C3—C4	−3.56 (19)	C4—C5—C6—C1	0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H711···O1ⁱ	0.89 (1)	2.41 (2)	3.1257 (14)	138 (2)
N2—H721···N1ⁱⁱ	0.88 (1)	2.26 (1)	3.0800 (16)	156 (2)
N2—H722···O1	0.88 (1)	1.98 (1)	2.6084 (14)	127 (1)
N2—H722···O1ⁱⁱⁱ	0.88 (1)	2.55 (2)	3.1416 (16)	126 (1)

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₆H₇N₃O₂
M_r	153.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	13.2854 (5), 3.7504 (1), 16.3309 (6)
β (°)	126.208 (2)
V (Å³)	656.55 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.55 × 0.24 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6477, 1605, 1262
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.115, 1.05
No. of reflections	1605
No. of parameters	113
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.17

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H711···O1ⁱ	0.887 (12)	2.409 (16)	3.1257 (14)	138.0 (15)
N2—H721···N1ⁱⁱ	0.880 (12)	2.255 (13)	3.0800 (16)	155.9 (15)
N2—H722···O1	0.878 (12)	1.980 (14)	2.6084 (14)	127.4 (14)
N2—H722···O1ⁱⁱⁱ	0.878 (12)	2.546 (15)	3.1416 (16)	125.8 (13)

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) −x, −y+1, −z.

Acknowledgements

The authors thank Mr Henk Schalekamp for helpful discussions.

References

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