4-Methyl­anilinium nitrate

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).

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.049
• wR factor = 0.125
• Data-to-parameter ratio = 25.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         44 Perc.

Alert level G
PLAT128_ALERT_4_G Non-standard setting of Space-group P21/c   ....      P21/n

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.96 Å (methyl) or 0.93 Å (aromatic) and N—H = 0.89 Å with U_iso(H) = 1.2U_eq(aromatic) or U_iso(H) = 1.5U_eq(methyl,N).

Computing details

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

	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

Crystal data

C7H10N^+·NO3^−	F(000) = 360
Mr = 170.17	Dx = 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) Å^3	0.2 × 0.15 × 0.1 mm
Z = 4

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.125	H-atom parameters constrained
S = 0.91	w = 1/[σ^2(Fo^2) + (0.0589P)^2] where P = (Fo^2 + 2Fc^2)/3
2791 reflections	(Δ/σ)max = 0.001
111 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O2^i	0.89	1.93	2.8208 (18)	177
N1—H1C···O3^ii	0.89	2.11	2.9461 (17)	157
N1—H1C···O2^ii	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.