4-Methyl­anilinium nitrate

Xu, R.

doi:10.1107/S1600536810005441

organic compounds

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doi:10.1107/S1600536810005441

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4-Methylanilinium nitrate

Rui-jun Xu ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: youyoubanzhen@126.com

(Received 22 August 2009; accepted 9 February 2010; online 13 March 2010)

In the crystal structure of the title compound, C₇H₁₀N⁺·NO₃⁻, N—H⋯O hydrogen bonds involving the ammonium group and the nitrate O atoms result in the formation of zigzag chains propagating in [100].

Related literature

For dielectric-ferroelectric materials, including organic ligands and metal-organic coordination compounds, see: Hang et al. (2009 ); Li et al. (2008 ).

Experimental

Crystal data

C₇H₁₀N⁺·NO₃⁻
M_r = 170.17
Monoclinic, P 2₁ /c
a = 5.6468 (11) Å
b = 8.7860 (18) Å
c = 17.811 (4) Å
β = 99.01 (3)°
V = 872.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.60 × 0.40 × 0.40 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.5, T_max = 0.5
8641 measured reflections
2011 independent reflections
1432 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.156
S = 1.01
2011 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.89	2.38	3.138 (3)	143
N1—H1A⋯O2ⁱ	0.89	2.13	2.975 (2)	158
N1—H1B⋯O1ⁱⁱ	0.89	1.97	2.848 (2)	171
N1—H1C⋯O2ⁱⁱⁱ	0.89	1.95	2.825 (2)	169
Symmetry codes: (i) x, y+1, z; (ii) x-1, y+1, z; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810005441/su2140sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810005441/su2140Isup2.hkl

checkCIF report

Comment top

As a part of systematic investigation of dielectric-ferroelectric materials, including organic ligands (Li et al., 2008), metal–organic coordination compounds (Hang et al., 2009), we have found that 4-methylbenzenaminium nitrate has no dielectric disuniform from 80 K to 445 K, (m.p. 465–468 K). Herein we descibe the crystal structure of this compound.

The asymmetric unit of the title compound consists of a 4-methylbenzenaminium cation and a nitrate anion (Fig. 1).

In the crystal N—H···O hydrogen bonds (Table 1) link the cations and anions to form chains propagating along the a axis (Fig 2).

Related literature top

For dielectric-ferroelectric materials, including organic ligands and metal-organic coordination compounds, see: Hang et al. (2009); Li et al. (2008).

Experimental top

The title compound was obtained by mixing p-toluidine and nitric acid in ethanol, in the stoichiometric ratio 1:1. After a few weeks, colorless crystals were obtained by slow evaporation.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the crystal packing of the title compound. The N—H···O hydrogen bonds are shown as dashed lines (see Table 1 for details).

4-Methylanilinium nitrate top

Crystal data top

C₇H₁₀N⁺·NO₃⁻	F(000) = 360
M_r = 170.17	D_x = 1.295 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3553 reflections
a = 5.6468 (11) Å	θ = 3.3–27.6°
b = 8.7860 (18) Å	µ = 0.10 mm⁻¹
c = 17.811 (4) Å	T = 298 K
β = 99.01 (3)°	Prism, colourless
V = 872.8 (3) Å³	0.60 × 0.40 × 0.40 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	2011 independent reflections
Radiation source: fine-focus sealed tube	1432 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
CCD profile fitting scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
T_min = 0.5, T_max = 0.5	l = −23→23
8641 measured reflections

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.156	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0752P)² + 0.2152P] where P = (F_o² + 2F_c²)/3
2011 reflections	(Δ/σ)_max < 0.001
111 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₇H₁₀N⁺·NO₃⁻	V = 872.8 (3) Å³
M_r = 170.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.6468 (11) Å	µ = 0.10 mm⁻¹
b = 8.7860 (18) Å	T = 298 K
c = 17.811 (4) Å	0.60 × 0.40 × 0.40 mm
β = 99.01 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2011 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1432 reflections with I > 2σ(I)
T_min = 0.5, T_max = 0.5	R_int = 0.038
8641 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.156	H-atom parameters constrained
S = 1.01	Δρ_max = 0.24 e Å⁻³
2011 reflections	Δρ_min = −0.26 e Å⁻³
111 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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
N1	0.3877 (3)	0.91687 (17)	0.33271 (9)	0.0512 (5)
C1	0.4679 (3)	0.83868 (18)	0.40462 (10)	0.0434 (5)
C2	0.6763 (3)	0.7554 (2)	0.41229 (12)	0.0658 (8)
C3	0.7515 (4)	0.6808 (2)	0.47979 (14)	0.0578 (7)
C4	0.6214 (4)	0.6858 (2)	0.53968 (12)	0.0607 (7)
C5	0.4132 (4)	0.7703 (2)	0.52945 (11)	0.0627 (7)
C6	0.3354 (3)	0.8472 (2)	0.46280 (11)	0.0542 (6)
C7	0.7061 (5)	0.6011 (3)	0.61266 (14)	0.0920 (10)
O1	0.9140 (3)	0.02956 (19)	0.33081 (10)	0.0803 (6)
O2	0.6445 (2)	0.17377 (18)	0.27222 (9)	0.0675 (5)
O3	0.9986 (3)	0.1724 (2)	0.24110 (9)	0.0737 (6)
N2	0.8567 (3)	0.12615 (18)	0.28068 (9)	0.0492 (5)
H1A	0.49500	0.98720	0.32520	0.0770*
H1B	0.24690	0.96120	0.33430	0.0770*
H1C	0.37240	0.84980	0.29480	0.0770*
H2	0.76490	0.74950	0.37260	0.0690*
H3	0.89360	0.62550	0.48540	0.0790*
H5	0.32260	0.77550	0.56870	0.0750*
H6	0.19500	0.90420	0.45730	0.0650*
H7A	0.57120	0.55570	0.63080	0.1380*
H7B	0.78420	0.67070	0.65010	0.1380*
H7C	0.81700	0.52300	0.60350	0.1380*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0498 (9)	0.0510 (9)	0.0537 (9)	−0.0069 (7)	0.0109 (7)	0.0010 (7)
C1	0.0431 (9)	0.0401 (9)	0.0470 (9)	−0.0087 (7)	0.0073 (7)	−0.0034 (7)
C2	0.0571 (12)	0.0555 (12)	0.0831 (15)	0.0059 (9)	0.0053 (11)	0.0088 (11)
C3	0.0526 (11)	0.0544 (11)	0.0700 (13)	0.0012 (9)	0.0206 (9)	0.0022 (9)
C4	0.0764 (14)	0.0453 (10)	0.0553 (11)	−0.0150 (10)	−0.0054 (10)	−0.0008 (8)
C5	0.0785 (14)	0.0653 (13)	0.0467 (11)	−0.0118 (11)	0.0175 (10)	−0.0070 (9)
C6	0.0521 (10)	0.0564 (11)	0.0555 (11)	0.0007 (9)	0.0126 (8)	−0.0059 (9)
C7	0.128 (2)	0.0688 (15)	0.0681 (15)	−0.0148 (15)	−0.0194 (15)	0.0106 (12)
O1	0.0720 (10)	0.0797 (10)	0.0930 (12)	0.0197 (8)	0.0244 (9)	0.0394 (9)
O2	0.0512 (8)	0.0811 (10)	0.0718 (10)	0.0102 (7)	0.0143 (7)	0.0174 (8)
O3	0.0618 (9)	0.0937 (12)	0.0703 (10)	−0.0148 (8)	0.0253 (7)	0.0113 (8)
N2	0.0489 (8)	0.0516 (8)	0.0478 (8)	−0.0026 (7)	0.0098 (6)	−0.0004 (7)

Geometric parameters (Å, º) top

O1—N2	1.238 (2)	C4—C5	1.378 (3)
O2—N2	1.256 (2)	C4—C7	1.509 (3)
O3—N2	1.217 (2)	C5—C6	1.377 (3)
N1—C1	1.461 (2)	C2—H2	0.9300
N1—H1A	0.8900	C3—H3	0.9300
N1—H1B	0.8900	C5—H5	0.9300
N1—H1C	0.8900	C6—H6	0.9300
C1—C6	1.372 (3)	C7—H7A	0.9600
C1—C2	1.374 (2)	C7—H7B	0.9600
C2—C3	1.377 (3)	C7—H7C	0.9600
C3—C4	1.387 (3)

H1B—N1—H1C	109.00	C4—C5—C6	121.92 (19)
C1—N1—H1B	109.00	C1—C6—C5	119.10 (17)
C1—N1—H1C	109.00	C3—C2—H2	121.00
C1—N1—H1A	109.00	C1—C2—H2	121.00
H1A—N1—H1C	109.00	C4—C3—H3	119.00
H1A—N1—H1B	109.00	C2—C3—H3	119.00
O1—N2—O2	116.86 (17)	C4—C5—H5	119.00
O2—N2—O3	121.45 (17)	C6—C5—H5	119.00
O1—N2—O3	121.70 (18)	C1—C6—H6	120.00
C2—C1—C6	120.92 (17)	C5—C6—H6	120.00
N1—C1—C6	120.37 (16)	C4—C7—H7C	109.00
N1—C1—C2	118.71 (17)	H7A—C7—H7C	109.00
C1—C2—C3	118.85 (19)	H7B—C7—H7C	109.00
C2—C3—C4	121.9 (2)	H7A—C7—H7B	109.00
C3—C4—C5	117.31 (19)	C4—C7—H7A	109.00
C3—C4—C7	120.8 (2)	C4—C7—H7B	109.00
C5—C4—C7	121.9 (2)

N1—C1—C2—C3	−179.58 (16)	C2—C3—C4—C5	−0.7 (3)
C6—C1—C2—C3	−0.4 (3)	C2—C3—C4—C7	179.1 (2)
N1—C1—C6—C5	178.92 (16)	C3—C4—C5—C6	0.0 (3)
C2—C1—C6—C5	−0.3 (3)	C7—C4—C5—C6	−179.8 (2)
C1—C2—C3—C4	0.9 (3)	C4—C5—C6—C1	0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.89	2.38	3.138 (3)	143
N1—H1A···O2ⁱ	0.89	2.13	2.975 (2)	158
N1—H1B···O1ⁱⁱ	0.89	1.97	2.848 (2)	171
N1—H1C···O2ⁱⁱⁱ	0.89	1.95	2.825 (2)	169

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

Experimental details

Crystal data
Chemical formula	C₇H₁₀N⁺·NO₃⁻
M_r	170.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	5.6468 (11), 8.7860 (18), 17.811 (4)
β (°)	99.01 (3)
V (Å³)	872.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.60 × 0.40 × 0.40

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.5, 0.5
No. of measured, independent and observed [I > 2σ(I)] reflections	8641, 2011, 1432
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.156, 1.01
No. of reflections	2011
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.26

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.89	2.38	3.138 (3)	143
N1—H1A···O2ⁱ	0.89	2.13	2.975 (2)	158
N1—H1B···O1ⁱⁱ	0.89	1.97	2.848 (2)	171
N1—H1C···O2ⁱⁱⁱ	0.89	1.95	2.825 (2)	169

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

References

Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Hang, T., Fu, D. W., Ye, Q. & Xiong, R. G. (2009). Cryst. Growth Des. 5, 2026–2029. Web of Science CSD CrossRef Google Scholar
Li, X. Z., Qu, Z. R. & Xiong, R. G. (2008). Chin. J. Chem. 11, 1959–1962. Web of Science CSD CrossRef Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o835

doi:10.1107/S1600536810005441

Open

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