5-Chloro-2-methoxy­anilinium nitrate

Hemissi, H.; Abid, S.; Rzaigui, M.

doi:10.1107/S1600536808008805

organic compounds

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Volume 64| Part 5| May 2008| Page o801

doi:10.1107/S1600536808008805

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5-Chloro-2-methoxyanilinium nitrate

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

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia
^*Correspondence e-mail: sonia.abid@fsb.rnu.tn

(Received 16 February 2008; accepted 1 April 2008; online 4 April 2008)

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, P 2₁ /c
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[F² > 2σ(F²)] = 0.041
wR(F²) = 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

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
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) x, y+1, z.

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 ).

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); 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).

Figures top

	Fig. 1. ORTEP-3 (Farrugia,(1999)) view of the title compound, with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level, and H-atoms are shown as spheres with an arbitary radius.
	Fig. 2. A perspective view of the atomic arrangement of the title compound.
	Fig. 3. Nitrate anion environment in the title compound. [Symmetry operators: (i) x, y, z; (ii) -x, y + 1/2, -z + 1/2; (iii) -x, -y, -z].

5-Chloro-2-methoxyanilinium nitrate top

Crystal data top

C₇H₉ClNO⁺·NO₃⁻	F(000) = 456
M_r = 220.61	D_x = 1.513 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 10.681 (2) Å	θ = 9.1–10.8°
b = 9.474 (3) Å	µ = 0.39 mm⁻¹
c = 9.802 (3) Å	T = 293 K
β = 102.38 (3)°	Prism, black
V = 968.8 (5) Å³	0.2 × 0.18 × 0.16 mm
Z = 4

Data collection top

Enraf–Nonius TurboCAD4 diffractometer	R_int = 0.029
Radiation source: Enraf–Nonius FR590	θ_max = 27.0°, θ_min = 2.9°
Graphite monochromator	h = −13→13
non–profiled ω scans	k = −12→0
4244 measured reflections	l = −12→12
2125 independent reflections	2 standard reflections every 120 min
1409 reflections with I > 2σ(I)	intensity decay: 5%

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0495P)² + 0.2112P] where P = (F_o² + 2F_c²)/3
2125 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₇H₉ClNO⁺·NO₃⁻	V = 968.8 (5) Å³
M_r = 220.61	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.681 (2) Å	µ = 0.39 mm⁻¹
b = 9.474 (3) Å	T = 293 K
c = 9.802 (3) Å	0.2 × 0.18 × 0.16 mm
β = 102.38 (3)°

Data collection top

Enraf–Nonius TurboCAD4 diffractometer	R_int = 0.029
4244 measured reflections	2 standard reflections every 120 min
2125 independent reflections	intensity decay: 5%
1409 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.02	Δρ_max = 0.18 e Å⁻³
2125 reflections	Δρ_min = −0.42 e Å⁻³
129 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
Cl	0.39657 (5)	0.59783 (8)	0.79445 (7)	0.0703 (2)
N2	0.83926 (16)	0.40697 (19)	0.75239 (18)	0.0478 (4)
H2	0.8415	0.3375	0.6918	0.072*
H1	0.8331	0.3705	0.8344	0.072*
H3	0.9107	0.4579	0.7630	0.072*
O4	0.83237 (15)	0.55493 (16)	0.52279 (16)	0.0568 (4)
C1	0.72828 (18)	0.4973 (2)	0.6998 (2)	0.0387 (4)
C2	0.72905 (19)	0.5751 (2)	0.5790 (2)	0.0425 (5)
C3	0.6254 (2)	0.6618 (2)	0.5276 (2)	0.0530 (6)
H4	0.6241	0.7158	0.4481	0.064*
C4	0.5237 (2)	0.6682 (2)	0.5941 (2)	0.0532 (5)
H5	0.4537	0.7256	0.5585	0.064*
C5	0.52562 (19)	0.5906 (2)	0.7117 (2)	0.0465 (5)
C6	0.62876 (18)	0.5041 (2)	0.7675 (2)	0.0425 (5)
H6	0.6303	0.4523	0.8484	0.051*
C7	0.8528 (3)	0.6480 (3)	0.4147 (3)	0.0714 (7)
H7	0.7883	0.6316	0.3316	0.107*
H8	0.9360	0.6309	0.3957	0.107*
H9	0.8477	0.7441	0.4443	0.107*
O1	0.82176 (15)	0.19146 (16)	0.53507 (16)	0.0556 (4)
N1	0.88696 (17)	0.09358 (19)	0.60238 (19)	0.0484 (4)
O2	0.8812 (2)	−0.02617 (18)	0.5536 (2)	0.0835 (6)
O3	0.95687 (16)	0.12025 (18)	0.71720 (17)	0.0648 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0462 (3)	0.0888 (5)	0.0816 (5)	−0.0011 (3)	0.0262 (3)	−0.0182 (4)
N2	0.0487 (9)	0.0465 (10)	0.0493 (10)	0.0074 (8)	0.0128 (8)	0.0016 (8)
O4	0.0608 (9)	0.0616 (10)	0.0553 (9)	0.0042 (8)	0.0284 (8)	0.0059 (8)
C1	0.0394 (9)	0.0342 (10)	0.0416 (10)	0.0017 (8)	0.0067 (8)	−0.0040 (8)
C2	0.0474 (11)	0.0390 (10)	0.0426 (11)	−0.0011 (9)	0.0133 (9)	−0.0051 (9)
C3	0.0641 (14)	0.0486 (13)	0.0465 (12)	0.0072 (11)	0.0123 (10)	0.0052 (10)
C4	0.0518 (12)	0.0508 (13)	0.0539 (13)	0.0117 (10)	0.0043 (10)	−0.0034 (11)
C5	0.0389 (10)	0.0487 (12)	0.0525 (12)	−0.0016 (9)	0.0112 (9)	−0.0156 (10)
C6	0.0465 (11)	0.0410 (11)	0.0411 (11)	−0.0061 (9)	0.0122 (9)	−0.0044 (9)
C7	0.0947 (19)	0.0575 (15)	0.0752 (17)	−0.0137 (14)	0.0481 (15)	−0.0009 (13)
O1	0.0598 (9)	0.0502 (9)	0.0562 (9)	0.0115 (8)	0.0108 (7)	0.0016 (7)
N1	0.0526 (10)	0.0451 (10)	0.0522 (11)	−0.0002 (9)	0.0215 (9)	−0.0025 (9)
O2	0.1170 (16)	0.0446 (10)	0.0859 (13)	0.0093 (10)	0.0152 (12)	−0.0144 (10)
O3	0.0709 (11)	0.0675 (11)	0.0518 (10)	0.0030 (8)	0.0038 (8)	−0.0049 (8)

Geometric parameters (Å, º) top

Cl—C5	1.744 (2)	C3—H4	0.9300
N2—C1	1.463 (2)	C4—C5	1.364 (3)
N2—H2	0.8900	C4—H5	0.9300
N2—H1	0.8900	C5—C6	1.388 (3)
N2—H3	0.8900	C6—H6	0.9300
O4—C2	1.349 (2)	C7—H7	0.9600
O4—C7	1.431 (3)	C7—H8	0.9600
C1—C6	1.370 (3)	C7—H9	0.9600
C1—C2	1.397 (3)	O1—N1	1.258 (2)
C2—C3	1.383 (3)	N1—O2	1.228 (2)
C3—C4	1.383 (3)	N1—O3	1.236 (2)

C1—N2—H2	109.5	C5—C4—H5	119.9
C1—N2—H1	109.5	C3—C4—H5	119.9
H2—N2—H1	109.5	C4—C5—C6	121.21 (19)
C1—N2—H3	109.5	C4—C5—Cl	120.13 (17)
H2—N2—H3	109.5	C6—C5—Cl	118.66 (17)
H1—N2—H3	109.5	C1—C6—C5	118.04 (19)
C2—O4—C7	118.86 (18)	C1—C6—H6	121.0
C6—C1—C2	122.12 (18)	C5—C6—H6	121.0
C6—C1—N2	120.77 (18)	O4—C7—H7	109.5
C2—C1—N2	117.11 (17)	O4—C7—H8	109.5
O4—C2—C3	126.62 (19)	H7—C7—H8	109.5
O4—C2—C1	115.18 (18)	O4—C7—H9	109.5
C3—C2—C1	118.19 (19)	H7—C7—H9	109.5
C4—C3—C2	120.2 (2)	H8—C7—H9	109.5
C4—C3—H4	119.9	O2—N1—O3	120.9 (2)
C2—C3—H4	119.9	O2—N1—O1	120.0 (2)
C5—C4—C3	120.3 (2)	O3—N1—O1	119.02 (18)

C7—O4—C2—C3	12.4 (3)	C2—C3—C4—C5	0.8 (3)
C7—O4—C2—C1	−168.9 (2)	C3—C4—C5—C6	0.1 (3)
C6—C1—C2—O4	−178.65 (18)	C3—C4—C5—Cl	−179.46 (17)
N2—C1—C2—O4	1.4 (3)	C2—C1—C6—C5	0.7 (3)
C6—C1—C2—C3	0.2 (3)	N2—C1—C6—C5	−179.35 (18)
N2—C1—C2—C3	−179.74 (18)	C4—C5—C6—C1	−0.9 (3)
O4—C2—C3—C4	177.7 (2)	Cl—C5—C6—C1	178.71 (15)
C1—C2—C3—C4	−1.0 (3)

Hydrogen-bond geometry (Å, º) top

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

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

Experimental details

Crystal data
Chemical formula	C₇H₉ClNO⁺·NO₃⁻
M_r	220.61
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.681 (2), 9.474 (3), 9.802 (3)
β (°)	102.38 (3)
V (Å³)	968.8 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.2 × 0.18 × 0.16

Data collection
Diffractometer	Enraf–Nonius TurboCAD4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4244, 2125, 1409
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.109, 1.02
No. of reflections	2125
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.42

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), DIAMOND (Brandenburg, 1998), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O1ⁱ	0.8900	2.0800	2.967 (3)	173
N2—H1···O2ⁱ	0.8900	2.5700	3.103 (3)	120
N2—H2···O1	0.8900	2.0400	2.927 (3)	171
N2—H2···O3	0.8900	2.3800	3.043 (3)	131
N2—H3···O2ⁱⁱ	0.8900	2.5500	3.240 (3)	135
N2—H3···O3ⁱⁱ	0.8900	2.0700	2.939 (3)	165
C7—H9···O2ⁱⁱⁱ	0.9600	2.4200	3.361 (4)	167

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

References

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