3-Nitro­benzene-1,2-diamine

Richard Betz; Thomas Gerber

doi:10.1107/S1600536811016825

. 2011 May 7;67(Pt 6):o1359. doi: 10.1107/S1600536811016825

3-Nitrobenzene-1,2-diamine

Richard Betz ^a,^*, Thomas Gerber ^a

PMCID: PMC3120524 PMID: 21754753

Abstract

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,
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[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 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

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 ▶).

Supplementary Material

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

e-67-o1359-sup1.cif^{(13.1KB, cif)}

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

e-67-o1359-Isup2.hkl^{(79.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811016825/sj5135Isup3.cml

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—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)

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

Acknowledgments

The authors thank Mr Henk Schalekamp for helpful discussions.

supplementary crystallographic information

Comment

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.

Experimental

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