4-Methyl­anilinium nitrate

Benali-Cherif, N.; Boussekine, H.; Boutobba, Z.; Dadda, N.

doi:10.1107/S1600536809041488

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2744

https://doi.org/10.1107/S1600536809041488

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4-Methylanilinium nitrate

Nourredine Benali-Cherif,^a ^* Houda Boussekine,^a Zina Boutobba ^a and Noureddine Dadda ^a

^aLaboratoire des Structures, Propriétés et Interactions Inter Atomiques (LASPI²A), Centre Universitaire Abbes Laghrour-Khenchela, 40000. Khenchela, Algeria
^*Correspondence e-mail: benalicherif@hotmail.com

(Received 10 September 2009; accepted 11 October 2009; online 17 October 2009)

The asymmetric unit of the title compound, C₇H₁₀N⁺·NO₃⁻, consists of a 4-methylanilinium cation protonated at the amino group and a nitrate anion. In the crystal, anions and cations are linked through N—H⋯O and N—H⋯(O,O) hydrogen bonds, buiding a corrugated layer structure parallel to (001).

Related literature

For related structures, see: Benali-Cherif, Kateb et al. (2007 ); Benali-Cherif, Allouche et al. (2007 ); Benali-Cherif, Boussekine et al. (2007 ); Asath Bahadur et al. (2007 ). For the biological effects of toluidine exposure in man, see: Kennedy et al. (1984 ).

Experimental

Crystal data

C₇H₁₀N⁺·NO₃⁻
M_r = 170.17
Monoclinic, P 2₁ /n
a = 5.6725 (9) Å
b = 8.5507 (8) Å
c = 17.621 (2) Å
β = 98.771 (2)°
V = 844.69 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.2 × 0.15 × 0.1 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
24550 measured reflections
2791 independent reflections
1228 reflections with I > 2σ(I)
R_int = 0.089

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.125
S = 0.91
2791 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O3	0.89	1.93	2.8032 (17)	167
N1—H1A⋯O2ⁱ	0.89	1.93	2.8208 (18)	177
N1—H1C⋯O3ⁱⁱ	0.89	2.11	2.9461 (17)	157
N1—H1C⋯O2ⁱⁱ	0.89	2.46	3.1726 (18)	138
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: KappaCCD (Nonius, 1998 ); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and CAMERON (Pearce et al., 2000 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809041488/dn2484sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809041488/dn2484Isup2.hkl

checkCIF report

Comment top

p-toluidine is an organic benzene derivative with a methyl substituent and an amino group, the name is derived from toluene and aniline. Its physical appearance is that of white lustrous plates or leaflets with an amine odour. p-toluidine can cause anoxia (due to formation of methemoglobin) and hematuria in man. The substance irritates the eyes and the skin and may cause effects on the blood, bladder and kidneys, resulting in tissue lesions and formation of methamoglobin (Kennedy et al., 1984). The crystal structure of p-methylanilinium nitrate, (I), was determined as part of our investigations on the structural characteristicsof organic-inorganic layered compounds and an ongoing study on D—H···A hydrogen-bonding in systems of hybrid materials including anilinium derivatives such as, 3-hydroxyanilinium hydrogensulfate (Benali-Cherif, Kateb et al., 2007), o-methylanilinium nitrate (Benali-Cherif, Boussekine et al., 2007), 2-carboxyanilinium dihydrogenphosphate (Benali-Cherif, Allouche et al., 2007) and 2-carboxyanilinium nitrate (Bahadur et al., 2007).

The asymmetric unit of (I) contains a monoprotonated p-methylanilinium cation and nitrate anion link trough N-H···O hydrogen bond (Figure 1). Intra atomic bond distances and angles confirm the monprotonation of the organic entity. There are differences in the N—O distances of nitrate anion N2—O2, N2–03 (1.260 (2) Å, 1.276 (2) Å) are longer than N2—O1 (1.232 (2) Å), this is the due that only the O2 and O3 atoms are involved in hydrogen bonds of types N—H ··· O. (Table 1). The structure of (C₇H₁₀N⁺. NO₃^-) is composed of cationic (C₇H₁₀N⁺) and anionic (NO₃^-) linked through N-H···O hydrogren bonds and building up a corrugated layers parallel to the (0 0 1) plane (Table 1, Figure 2).

Related literature top

For related structures, see: Benali-Cherif, Kateb et al. (2007); Benali-Cherif, Allouche et al. (2007); Benali-Cherif, Boussekine et al. (2007); Asath Bahadur et al. (2007). For the biological effects of toluidine exposure in man, see: Kennedy et al. (1984).

Experimental top

Single crystals of the title compound are prepared by slow evaporation at room temperature of an aqueous solution of p-methylaniline (C₇H₉N) and nitric acid in the stoichiometric ratio 1:1.

Structure description top

For related structures, see: Benali-Cherif, Kateb et al. (2007); Benali-Cherif, Allouche et al. (2007); Benali-Cherif, Boussekine et al. (2007); Asath Bahadur et al. (2007). For the biological effects of toluidine exposure in man, see: Kennedy et al. (1984).

Computing details top

Data collection: KappaCCD (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and CAMERON (Pearce et al., 2000); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Molecular view of compound I with the atom labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small sphere of arbitray radii. Hydrogen bond is shown as dashed line.
	Fig. 2. Partial packing view of the hydrogen-bonding network.

4-Methylanilinium nitrate top

Crystal data top

C₇H₁₀N⁺·NO₃⁻	F(000) = 360
M_r = 170.17	D_x = 1.338 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 24550 reflections
a = 5.6725 (9) Å	θ = 2.7–31.5°
b = 8.5507 (8) Å	µ = 0.11 mm⁻¹
c = 17.621 (2) Å	T = 100 K
β = 98.771 (2)°	Prism, brown
V = 844.69 (18) Å³	0.2 × 0.15 × 0.1 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	1228 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.089
Graphite monochromator	θ_max = 31.5°, θ_min = 2.7°
ω–θ scans	h = −8→5
24550 measured reflections	k = −12→12
2791 independent reflections	l = −25→25

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H-atom parameters constrained
S = 0.91	w = 1/[σ²(F_o²) + (0.0589P)²] where P = (F_o² + 2F_c²)/3
2791 reflections	(Δ/σ)_max = 0.001
111 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₇H₁₀N⁺·NO₃⁻	V = 844.69 (18) Å³
M_r = 170.17	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.6725 (9) Å	µ = 0.11 mm⁻¹
b = 8.5507 (8) Å	T = 100 K
c = 17.621 (2) Å	0.2 × 0.15 × 0.1 mm
β = 98.771 (2)°

Data collection top

Nonius KappaCCD diffractometer	1228 reflections with I > 2σ(I)
24550 measured reflections	R_int = 0.089
2791 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 0.91	Δρ_max = 0.29 e Å⁻³
2791 reflections	Δρ_min = −0.19 e Å⁻³
111 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.4327 (3)	0.15225 (17)	0.90563 (9)	0.0212 (4)
C2	0.2258 (3)	0.23416 (18)	0.91199 (10)	0.0251 (4)
H2	0.0979	0.2342	0.8721	0.030*
C3	0.2140 (3)	0.31609 (19)	0.97933 (10)	0.0280 (4)
H3	0.0752	0.3705	0.9843	0.034*
C4	0.4025 (3)	0.31936 (17)	1.03941 (10)	0.0261 (4)
C5	0.6101 (3)	0.23714 (18)	1.03075 (9)	0.0265 (4)
H5	0.7396	0.2386	1.0701	0.032*
C6	0.6249 (3)	0.15283 (17)	0.96364 (9)	0.0239 (4)
H6	0.7629	0.0979	0.9583	0.029*
C7	0.3867 (4)	0.4121 (2)	1.11156 (10)	0.0347 (5)
H7A	0.4333	0.5184	1.1044	0.052*
H7B	0.4911	0.3670	1.1539	0.052*
H7C	0.2257	0.4099	1.1222	0.052*
N1	0.4466 (2)	0.06544 (14)	0.83447 (7)	0.0236 (3)
H1A	0.5927	0.0263	0.8361	0.035*
H1B	0.4147	0.1296	0.7945	0.035*
H1C	0.3409	−0.0122	0.8298	0.035*
N2	0.5736 (3)	0.35591 (15)	0.71667 (8)	0.0249 (3)
O1	0.7537 (2)	0.31274 (13)	0.75970 (7)	0.0311 (3)
O2	0.5852 (2)	0.45260 (13)	0.66347 (7)	0.0339 (3)
O3	0.3676 (2)	0.30432 (13)	0.72457 (7)	0.0295 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0282 (9)	0.0117 (7)	0.0233 (9)	−0.0041 (7)	0.0031 (7)	0.0006 (6)
C2	0.0245 (9)	0.0180 (8)	0.0312 (10)	−0.0018 (7)	−0.0012 (7)	0.0002 (7)
C3	0.0290 (10)	0.0182 (8)	0.0373 (11)	0.0018 (7)	0.0066 (8)	−0.0007 (7)
C4	0.0381 (10)	0.0130 (7)	0.0285 (10)	−0.0053 (7)	0.0095 (8)	0.0016 (7)
C5	0.0333 (10)	0.0207 (8)	0.0241 (10)	−0.0042 (7)	0.0001 (8)	0.0029 (7)
C6	0.0261 (9)	0.0167 (8)	0.0291 (10)	0.0000 (7)	0.0051 (7)	0.0036 (7)
C7	0.0524 (12)	0.0222 (8)	0.0305 (11)	−0.0023 (8)	0.0097 (9)	−0.0023 (7)
N1	0.0277 (8)	0.0166 (6)	0.0260 (8)	−0.0014 (6)	0.0022 (6)	0.0002 (6)
N2	0.0290 (8)	0.0169 (7)	0.0279 (8)	0.0011 (6)	0.0018 (7)	−0.0022 (6)
O1	0.0276 (7)	0.0305 (7)	0.0326 (7)	0.0051 (6)	−0.0038 (6)	0.0023 (6)
O2	0.0354 (7)	0.0252 (6)	0.0397 (8)	−0.0020 (6)	0.0008 (6)	0.0139 (6)
O3	0.0277 (7)	0.0267 (6)	0.0338 (7)	−0.0015 (5)	0.0041 (5)	0.0052 (5)

Geometric parameters (Å, º) top

C1—C6	1.376 (2)	C6—H6	0.9300
C1—C2	1.386 (2)	C7—H7A	0.9600
C1—N1	1.470 (2)	C7—H7B	0.9600
C2—C3	1.388 (2)	C7—H7C	0.9600
C2—H2	0.9300	N1—H1A	0.8900
C3—C4	1.385 (2)	N1—H1B	0.8900
C3—H3	0.9300	N1—H1C	0.8900
C4—C5	1.399 (2)	N2—O1	1.2325 (17)
C4—C7	1.513 (2)	N2—O2	1.2592 (16)
C5—C6	1.398 (2)	N2—O3	1.2759 (17)
C5—H5	0.9300

C6—C1—C2	121.53 (15)	C5—C6—H6	120.4
C6—C1—N1	119.74 (14)	C4—C7—H7A	109.5
C2—C1—N1	118.73 (14)	C4—C7—H7B	109.5
C1—C2—C3	118.41 (16)	H7A—C7—H7B	109.5
C1—C2—H2	120.8	C4—C7—H7C	109.5
C3—C2—H2	120.8	H7A—C7—H7C	109.5
C4—C3—C2	122.09 (16)	H7B—C7—H7C	109.5
C4—C3—H3	119.0	C1—N1—H1A	109.5
C2—C3—H3	119.0	C1—N1—H1B	109.5
C3—C4—C5	118.08 (16)	H1A—N1—H1B	109.5
C3—C4—C7	121.01 (16)	C1—N1—H1C	109.5
C5—C4—C7	120.90 (17)	H1A—N1—H1C	109.5
C6—C5—C4	120.75 (16)	H1B—N1—H1C	109.5
C6—C5—H5	119.6	O1—N2—O2	121.47 (14)
C4—C5—H5	119.6	O1—N2—O3	121.07 (14)
C1—C6—C5	119.14 (16)	O2—N2—O3	117.45 (14)
C1—C6—H6	120.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3	0.89	1.93	2.8032 (17)	167
N1—H1A···O2ⁱ	0.89	1.93	2.8208 (18)	177
N1—H1C···O3ⁱⁱ	0.89	2.11	2.9461 (17)	157
N1—H1C···O2ⁱⁱ	0.89	2.46	3.1726 (18)	138

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

Experimental details

Crystal data
Chemical formula	C₇H₁₀N⁺·NO₃⁻
M_r	170.17
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	5.6725 (9), 8.5507 (8), 17.621 (2)
β (°)	98.771 (2)
V (Å³)	844.69 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.2 × 0.15 × 0.1

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	24550, 2791, 1228
R_int	0.089
(sin θ/λ)_max (Å⁻¹)	0.735

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.125, 0.91
No. of reflections	2791
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.19

Computer programs: KappaCCD (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and CAMERON (Pearce et al., 2000), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3	0.89	1.93	2.8032 (17)	167.2
N1—H1A···O2ⁱ	0.89	1.93	2.8208 (18)	176.6
N1—H1C···O3ⁱⁱ	0.89	2.11	2.9461 (17)	157.3
N1—H1C···O2ⁱⁱ	0.89	2.46	3.1726 (18)	137.8

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

Acknowledgements

We wish to thank Dr C. Lecomte, Dr S. Dahaoui and Dr E.-E. Bendeif, LCM³B (UMR UHP–CNRS 7036), Faculté des Sciences et Techniques 54506 Vandoeuvre-lés-Nancy CEDEX, for providing diffraction facilities, and le Centre Universitaire Abbes Laghrour-Khenchela for financial support.

References

Bahadur, S. A., Kannan, R. S. & Sridhar, B. (2007). Acta Cryst. E63, o2722–o2723. Web of Science CSD CrossRef IUCr Journals Google Scholar
Benali-Cherif, N., Allouche, F., Direm, A., Boukli-H-Benmenni, L. & Soudani, K. (2007). Acta Cryst. E63, o2643–o2645. Web of Science CSD CrossRef IUCr Journals Google Scholar
Benali-Cherif, N., Boussekine, H., Boutobba, Z. & Kateb, A. (2007). Acta Cryst. E63, o3287. Web of Science CSD CrossRef IUCr Journals Google Scholar
Benali-Cherif, N., Kateb, A., Boussekine, H., Boutobba, Z. & Messai, A. (2007). Acta Cryst. E63, o3251. Web of Science CSD CrossRef IUCr Journals Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Kennedy, G. L., Chen, H. C. & Hall, G. T. (1984). Food Chem. Toxicol. 22, 289–292. CrossRef CAS PubMed Web of Science Google Scholar
Nonius (1998). KappaCCD Server Software. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Pearce, L., Prout, C. K. & Watkin, D. J. (2000). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar