5-Chloro-2-methoxy­anilinium nitrate

Hanene Hemissi; Sonia Abid; Mohamed Rzaigui

doi:10.1107/S1600536808008805

. 2008 Apr 4;64(Pt 5):o801. doi: 10.1107/S1600536808008805

5-Chloro-2-methoxyanilinium nitrate

Hanene Hemissi ^a, Sonia Abid ^a,^*, Mohamed Rzaigui ^a

PMCID: PMC2961331 PMID: 21202293

Abstract

The title salt, C₇H₉ClNO⁺·NO₃ ⁻, exhibits extensive hydrogen bonding between the ammonium functional group and the nitrate anion. A two-dimensional network of bifurcated N—H⋯O hydrogen bonds generates corrugated layers in the bc plane. The organic molecules are stacked in a parallel orientation as a result of π–π interactions, with an inter-ring distance of 3.837 Å.

Related literature

For related literature, see: Abid et al. (2007 ▶); Aloui et al. (2002 ▶); Desiraju & Steiner (1999 ▶); Hemissi et al. (2005 ▶); Jayaraman et al. (2002 ▶); Ouslati & Ben Nasr (2006 ▶); Steiner (2002 ▶); Kefi et al. (2007 ▶).

Experimental

Crystal data

C₇H₉ClNO⁺·NO₃ ⁻
M _r = 220.61
Monoclinic,
a = 10.681 (2) Å
b = 9.474 (3) Å
c = 9.802 (3) Å
β = 102.38 (3)°
V = 968.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 293 (2) K
0.2 × 0.18 × 0.16 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction: none
4244 measured reflections
2125 independent reflections
1409 reflections with I > 2σ(I)
R _int = 0.029
2 standard reflections frequency: 120 min intensity decay: 5%

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.109
S = 1.02
2125 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶), DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808008805/fj2102sup1.cif

e-64-0o801-sup1.cif^{(15.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808008805/fj2102Isup2.hkl

e-64-0o801-Isup2.hkl^{(102.4KB, 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
N2—H1⋯O1ⁱ	0.89	2.08	2.967 (3)	173
N2—H1⋯O2ⁱ	0.89	2.57	3.103 (3)	120
N2—H2⋯O1	0.89	2.04	2.927 (3)	171
N2—H2⋯O3	0.89	2.38	3.043 (3)	131
N2—H3⋯O2ⁱⁱ	0.89	2.55	3.240 (3)	135
N2—H3⋯O3ⁱⁱ	0.89	2.07	2.939 (3)	165
C7—H9⋯O2ⁱⁱⁱ	0.96	2.42	3.361 (4)	167

Open in a new tab

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

supplementary crystallographic information

Comment

Hydrogen bonding is of intense interest because of their widespread occurrence in biological systems. So, it is very helpful to search simple molecules allowing to understanding the configuration and the function of some complex macromolecules.The hybrid compounds are rich in H-bonds and they could be used to this effect because of their potential importance in constructing sophisticated assemblies from discrete ionic or molecular building blocks due to its strength and directionality (Steiner. et al. 2002, Jayaraman, et al. 2002). In this work, the combination of 2-methoxy-5-chloroaniline and nitric acid has been chosen to elaborate the special hydrogen-bond pattern. The asymmetric unit of crystal structure, depicted in ORTEP drawing (Fig. 1), correspond to the formula unit C₆H₉ClNO⁺.NO₃^-. The main feature of this atomic arrangement is the existence of thick inorganic corrugated layers spreading around bc plane (Fig. 2). Inside layer, each NO₃^- anion is linked to three organic groups through bifurcated N–H···O H-bonding. The N···O and H···O bond lengths are in the ranges of 2.927 (3)–3.240 (3) Å and 2.04–2.57 Å, respectively. The organic species interact also with a weak C–H···O hydrogen bond with H···O separation of 2.42 Å. These interactions are weaker than those observed otherwise (Ouslati et al. 2006, Kefi et al. 2007). The orientation of molecules in this framework is governed by a nearly regular triangular arrangement of 2-methoxy-5-chlorophenylammonium groups [N···N distances between nitrogen ammonium atoms are in the range of 5.597 and 5.857 Å, N···N···N angles range from 57.75 to 62.25°] (Fig. 3). As well as electrostatic and van der Waals forces and hydrogen bonds, aromatic π-π stacking interactions participate to define the crystal packing. Indeed, in the atomic arrangement of the title compound, the phenyl ring of the organic molecules are stacked in the parallel orientation with inter-planar separation of 3.837 Å indicating there are π–π stacking interactions (Desiraju & Steiner, 1999). The –Cl, –NH₃ and –OCH₃ substituents form, respectively, different torsion angles with the benzene ring: Cl—C5—C6—C1 ((t1) = 178.71°), N2—C1—C2—C3 ((t2) = -179.74°) and C7—O4—C2—C3 ((t3) = 12.43°). (t1) and (t2) angle values show that the chloro and amino substituents are nearly coplanar with the aryl ring. The torsion angle (t3) value indicates that the methoxy group lies out the plane of the benzene ring. This conformation resembles that observed in other compounds (Abid et al. 2007, Aloui et al. 2002, Hemissi et al. 2005).

Experimental

An ethanolic 2-methoxy-5-chloroaniline solution (5 mmol, in 5 ml) was added to an aqueous HNO₃ solution (0.5 M). The obtained solution is evaporated during several days in ambient condition until the formation of single crystals of the title compound.