4-Methyl­anilinium p-toluene­sulfonate

Xu, R.

doi:10.1107/S1600536810021537

organic compounds

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Volume 66| Part 7| July 2010| Page o1794

doi:10.1107/S1600536810021537

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4-Methylanilinium p-toluenesulfonate

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 18 May 2010; accepted 6 June 2010; online 26 June 2010)

The crystal structure of the title compound, C₇H₁₀N⁺·C₇H₇O₃S⁻, displays strong N—H⋯O and N—H⋯S hydrogen bonding between the ammonium group and the p-toluenesulfonate anion, linking the cations and anions into chains along the b axis.

Related literature

For background to dielectric–ferroelectric materials, see: Hang et al. (2009 ); Li et al. (2008 ).

Experimental

Crystal data

C₇H₁₀N⁺·C₇H₇O₃S⁻
M_r = 279.35
Monoclinic, P 2₁
a = 5.775 (4) Å
b = 9.026 (5) Å
c = 13.350 (8) Å
β = 96.344 (9)°
V = 691.6 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 K
0.2 × 0.2 × 0.2 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.929, T_max = 1.000
6641 measured reflections
3136 independent reflections
2876 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.093
S = 0.99
3136 reflections
174 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ), 1448 Friedel pairs
Flack parameter: 0.05 (8)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯O1ⁱ	0.89	2.31	3.170 (3)	164
N1—H1D⋯O2ⁱ	0.89	2.33	2.824 (3)	115
N1—H1D⋯S1ⁱ	0.89	2.81	3.570 (3)	144
N1—H1E⋯O1ⁱⁱ	0.89	1.96	2.829 (3)	165
N1—H1F⋯O3ⁱⁱⁱ	0.89	2.02	2.785 (3)	143
Symmetry codes: (i) $[-x-1, y-{\script{1\over 2}}, -z+1]$ ; (ii) x-1, y-1, z; (iii) $[-x, y-{\script{1\over 2}}, -z+1]$ .

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/S1600536810021537/fj2307sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810021537/fj2307Isup2.hkl

checkCIF report

Comment top

Dielectric-ferroelectric as an interesting class of materials, there are organic ligands (Li et al., 2008), metal-organic coordination compounds (Hang et al., 2009) and organic-inorganic hybrid. In this article, the preparation and crystal structure of the title compound have been presented. It should be not a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range. Similarly, below the melting point (477 K) of the compound, the dielectric constant as a function of temperature also goes smoothly, and there is no dielectric anomaly observed.

The asymmetric unit of the title compound contains a (CH₃—C₆H₄—NH₃⁺) cation and an (CH₃—C₆H₄—SO₃^-) anion (Fig.1). The strong N—H···S, N—H···O hydrogen bonds involving H1D and H1E (N1···S1 3.570 (3) Å and N1···O1 2.829 (3) Å) are beneficial to the stability of the crystal structure and link the cations and anions to chains along the b axis (Fig. 2 and Tab. 1).

Related literature top

For background to dielectric–ferroelectric materials, see: Hang et al. (2009); Li et al. (2008)

Experimental top

The title compound was obtained by the addition of p-toluenesulfonic acid (3.78 g, 0.022 mol) to a solution of 4-methylaniline (2.14 g, 0.02 mol) in ethanol, in the stoichiometric ratio 1.1:1. After two weeks, good quality single 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: SHELXXL (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 packing of the title compound, stacking along the b axis. Dashed lines indicate hydrogen bonds.

4-Methylanilinium p-toluenesulfonate top

Crystal data top

C₇H₁₀N⁺·C₇H₇O₃S⁻	F(000) = 296
M_r = 279.35	D_x = 1.341 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3136 reflections
a = 5.775 (4) Å	θ = 3.6–27.5°
b = 9.026 (5) Å	µ = 0.24 mm⁻¹
c = 13.350 (8) Å	T = 293 K
β = 96.344 (9)°	Prism, colorless
V = 691.6 (7) Å³	0.2 × 0.2 × 0.2 mm
Z = 2

Data collection top

Rigaku Mercury2 diffractometer	3136 independent reflections
Radiation source: fine-focus sealed tube	2876 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.6°
CCD_Profile_fitting scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
T_min = 0.929, T_max = 1.000	l = −17→17
6641 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.0447P)² + 0.128P] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max < 0.001
3136 reflections	Δρ_max = 0.18 e Å⁻³
174 parameters	Δρ_min = −0.23 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1448 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (8)

Crystal data top

C₇H₁₀N⁺·C₇H₇O₃S⁻	V = 691.6 (7) Å³
M_r = 279.35	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 5.775 (4) Å	µ = 0.24 mm⁻¹
b = 9.026 (5) Å	T = 293 K
c = 13.350 (8) Å	0.2 × 0.2 × 0.2 mm
β = 96.344 (9)°

Data collection top

Rigaku Mercury2 diffractometer	3136 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2876 reflections with I > 2σ(I)
T_min = 0.929, T_max = 1.000	R_int = 0.029
6641 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.093	Δρ_max = 0.18 e Å⁻³
S = 0.99	Δρ_min = −0.23 e Å⁻³
3136 reflections	Absolute structure: Flack (1983), 1448 Friedel pairs
174 parameters	Absolute structure parameter: 0.05 (8)
1 restraint

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
S1	0.14320 (9)	−0.16236 (6)	0.34803 (4)	0.03362 (14)
O1	0.0753 (3)	−0.0673 (2)	0.42886 (12)	0.0456 (4)
O2	0.0234 (3)	−0.30349 (19)	0.34704 (14)	0.0481 (4)
O3	0.3936 (2)	−0.1756 (2)	0.34883 (12)	0.0485 (4)
C8	0.0436 (3)	−0.0720 (2)	0.23353 (15)	0.0302 (4)
C9	0.1872 (4)	0.0278 (3)	0.19156 (17)	0.0363 (5)
H9A	0.3372	0.0450	0.2223	0.044*
C10	0.1071 (4)	0.1023 (3)	0.10348 (19)	0.0420 (6)
H10A	0.2038	0.1701	0.0761	0.050*
C11	−0.1161 (4)	0.0769 (3)	0.05557 (17)	0.0394 (5)
C12	−0.2047 (5)	0.1588 (4)	−0.0397 (2)	0.0589 (8)
H12A	−0.3718	0.1546	−0.0491	0.071*
H12B	−0.1434	0.1134	−0.0962	0.071*
H12C	−0.1553	0.2603	−0.0343	0.071*
C13	−0.2562 (4)	−0.0238 (3)	0.09898 (18)	0.0405 (6)
H13A	−0.4056	−0.0420	0.0679	0.049*
C14	−0.1806 (4)	−0.0981 (3)	0.18702 (18)	0.0368 (5)
H14A	−0.2783	−0.1647	0.2149	0.044*
N1	−0.7130 (4)	−0.8010 (3)	0.50369 (16)	0.0513 (5)
H1D	−0.8346	−0.7437	0.5125	0.062*
H1E	−0.7621	−0.8925	0.4885	0.062*
H1F	−0.6154	−0.8026	0.5602	0.062*
C1	−0.2340 (5)	−0.5599 (4)	0.1861 (2)	0.0590 (7)
H1A	−0.2324	−0.4538	0.1911	0.071*
H1B	−0.3120	−0.5889	0.1218	0.071*
H1C	−0.0768	−0.5963	0.1926	0.071*
C2	−0.3611 (4)	−0.6242 (2)	0.26934 (18)	0.0408 (6)
C3	−0.2853 (4)	−0.7531 (3)	0.31786 (18)	0.0400 (5)
H3A	−0.1548	−0.8010	0.2985	0.048*
C4	−0.3986 (4)	−0.8132 (3)	0.39495 (18)	0.0392 (5)
H4A	−0.3448	−0.8996	0.4275	0.047*
C5	−0.5937 (4)	−0.7409 (3)	0.42196 (17)	0.0385 (5)
C6	−0.6736 (4)	−0.6122 (3)	0.3749 (2)	0.0485 (7)
H6A	−0.8047	−0.5645	0.3939	0.058*
C7	−0.5565 (5)	−0.5552 (3)	0.2994 (2)	0.0508 (6)
H7A	−0.6097	−0.4680	0.2677	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0322 (2)	0.0360 (3)	0.0334 (3)	0.0060 (3)	0.00711 (18)	0.0046 (2)
O1	0.0537 (10)	0.0513 (11)	0.0326 (9)	0.0096 (9)	0.0085 (7)	−0.0025 (8)
O2	0.0532 (11)	0.0334 (9)	0.0589 (11)	0.0011 (8)	0.0121 (8)	0.0090 (8)
O3	0.0311 (7)	0.0656 (11)	0.0489 (9)	0.0115 (9)	0.0046 (6)	0.0178 (9)
C8	0.0276 (10)	0.0320 (11)	0.0315 (10)	0.0028 (9)	0.0058 (8)	−0.0017 (9)
C9	0.0309 (11)	0.0432 (13)	0.0349 (12)	−0.0018 (10)	0.0044 (9)	0.0023 (10)
C10	0.0416 (13)	0.0448 (14)	0.0409 (13)	−0.0050 (11)	0.0101 (10)	0.0068 (11)
C11	0.0438 (12)	0.0443 (13)	0.0303 (11)	0.0072 (11)	0.0042 (10)	0.0023 (10)
C12	0.0641 (18)	0.074 (2)	0.0371 (14)	0.0073 (16)	0.0010 (12)	0.0134 (14)
C13	0.0295 (11)	0.0532 (15)	0.0380 (12)	0.0016 (11)	−0.0004 (9)	−0.0003 (11)
C14	0.0305 (11)	0.0392 (12)	0.0415 (13)	−0.0011 (10)	0.0071 (9)	0.0019 (10)
N1	0.0401 (11)	0.0737 (14)	0.0412 (11)	−0.0133 (11)	0.0088 (9)	−0.0154 (11)
C1	0.0736 (19)	0.0558 (17)	0.0486 (16)	−0.0024 (16)	0.0105 (14)	0.0017 (14)
C2	0.0469 (13)	0.0390 (14)	0.0362 (12)	−0.0028 (10)	0.0027 (10)	−0.0083 (9)
C3	0.0349 (12)	0.0416 (14)	0.0444 (13)	0.0025 (10)	0.0085 (10)	−0.0099 (11)
C4	0.0392 (12)	0.0377 (12)	0.0402 (12)	0.0013 (10)	0.0026 (9)	−0.0019 (10)
C5	0.0310 (11)	0.0513 (14)	0.0333 (11)	−0.0057 (10)	0.0047 (9)	−0.0119 (11)
C6	0.0385 (13)	0.0572 (16)	0.0494 (15)	0.0153 (11)	0.0032 (11)	−0.0145 (12)
C7	0.0583 (16)	0.0456 (15)	0.0474 (14)	0.0186 (13)	0.0012 (12)	−0.0013 (12)

Geometric parameters (Å, º) top

S1—O2	1.449 (2)	N1—C5	1.458 (3)
S1—O3	1.4500 (18)	N1—H1D	0.8903
S1—O1	1.4655 (18)	N1—H1E	0.8893
S1—C8	1.772 (2)	N1—H1F	0.8904
C8—C9	1.384 (3)	C1—C2	1.514 (4)
C8—C14	1.393 (3)	C1—H1A	0.9600
C9—C10	1.389 (3)	C1—H1B	0.9600
C9—H9A	0.9300	C1—H1C	0.9600
C10—C11	1.393 (4)	C2—C3	1.379 (3)
C10—H10A	0.9300	C2—C7	1.387 (4)
C11—C13	1.386 (3)	C3—C4	1.389 (3)
C11—C12	1.510 (3)	C3—H3A	0.9300
C12—H12A	0.9600	C4—C5	1.384 (3)
C12—H12B	0.9600	C4—H4A	0.9300
C12—H12C	0.9600	C5—C6	1.376 (4)
C13—C14	1.381 (3)	C6—C7	1.374 (4)
C13—H13A	0.9300	C6—H6A	0.9300
C14—H14A	0.9300	C7—H7A	0.9300

O2—S1—O3	113.73 (12)	C5—N1—H1D	109.1
O2—S1—O1	110.78 (11)	C5—N1—H1E	109.9
O3—S1—O1	113.02 (11)	H1D—N1—H1E	109.5
O2—S1—C8	106.72 (11)	C5—N1—H1F	109.4
O3—S1—C8	105.82 (10)	H1D—N1—H1F	109.4
O1—S1—C8	106.15 (11)	H1E—N1—H1F	109.5
C9—C8—C14	119.9 (2)	C2—C1—H1A	109.5
C9—C8—S1	119.82 (16)	C2—C1—H1B	109.5
C14—C8—S1	120.26 (17)	H1A—C1—H1B	109.5
C8—C9—C10	120.0 (2)	C2—C1—H1C	109.5
C8—C9—H9A	120.0	H1A—C1—H1C	109.5
C10—C9—H9A	120.0	H1B—C1—H1C	109.5
C9—C10—C11	120.9 (2)	C3—C2—C7	118.0 (2)
C9—C10—H10A	119.5	C3—C2—C1	120.9 (2)
C11—C10—H10A	119.5	C7—C2—C1	121.1 (2)
C13—C11—C10	118.0 (2)	C2—C3—C4	121.8 (2)
C13—C11—C12	120.9 (2)	C2—C3—H3A	119.1
C10—C11—C12	121.1 (2)	C4—C3—H3A	119.1
C11—C12—H12A	109.5	C5—C4—C3	118.2 (2)
C11—C12—H12B	109.5	C5—C4—H4A	120.9
H12A—C12—H12B	109.5	C3—C4—H4A	120.9
C11—C12—H12C	109.5	C6—C5—C4	121.4 (2)
H12A—C12—H12C	109.5	C6—C5—N1	119.6 (2)
H12B—C12—H12C	109.5	C4—C5—N1	119.0 (2)
C14—C13—C11	122.0 (2)	C7—C6—C5	118.9 (2)
C14—C13—H13A	119.0	C7—C6—H6A	120.5
C11—C13—H13A	119.0	C5—C6—H6A	120.5
C13—C14—C8	119.2 (2)	C6—C7—C2	121.8 (2)
C13—C14—H14A	120.4	C6—C7—H7A	119.1
C8—C14—H14A	120.4	C2—C7—H7A	119.1

O2—S1—C8—C9	−151.80 (18)	C11—C13—C14—C8	−0.4 (4)
O3—S1—C8—C9	−30.3 (2)	C9—C8—C14—C13	0.3 (3)
O1—S1—C8—C9	90.00 (19)	S1—C8—C14—C13	178.57 (18)
O2—S1—C8—C14	29.9 (2)	C7—C2—C3—C4	−0.2 (3)
O3—S1—C8—C14	151.35 (19)	C1—C2—C3—C4	179.5 (2)
O1—S1—C8—C14	−88.3 (2)	C2—C3—C4—C5	0.6 (3)
C14—C8—C9—C10	0.3 (3)	C3—C4—C5—C6	−0.6 (3)
S1—C8—C9—C10	−178.00 (19)	C3—C4—C5—N1	−179.1 (2)
C8—C9—C10—C11	−0.7 (4)	C4—C5—C6—C7	0.2 (4)
C9—C10—C11—C13	0.6 (4)	N1—C5—C6—C7	178.6 (2)
C9—C10—C11—C12	179.4 (2)	C5—C6—C7—C2	0.3 (4)
C10—C11—C13—C14	0.0 (4)	C3—C2—C7—C6	−0.2 (4)
C12—C11—C13—C14	−178.8 (2)	C1—C2—C7—C6	−179.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···O1ⁱ	0.89	2.31	3.170 (3)	164
N1—H1D···O2ⁱ	0.89	2.33	2.824 (3)	115
N1—H1D···S1ⁱ	0.89	2.81	3.570 (3)	144
N1—H1E···O1ⁱⁱ	0.89	1.96	2.829 (3)	165
N1—H1F···O3ⁱⁱⁱ	0.89	2.02	2.785 (3)	143

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

Experimental details

Crystal data
Chemical formula	C₇H₁₀N⁺·C₇H₇O₃S⁻
M_r	279.35
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	5.775 (4), 9.026 (5), 13.350 (8)
β (°)	96.344 (9)
V (Å³)	691.6 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.929, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6641, 3136, 2876
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.093, 0.99
No. of reflections	3136
No. of parameters	174
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.23
Absolute structure	Flack (1983), 1448 Friedel pairs
Absolute structure parameter	0.05 (8)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···O1ⁱ	0.89	2.31	3.170 (3)	164
N1—H1D···O2ⁱ	0.89	2.33	2.824 (3)	115
N1—H1D···S1ⁱ	0.89	2.81	3.570 (3)	144
N1—H1E···O1ⁱⁱ	0.89	1.96	2.829 (3)	165
N1—H1F···O3ⁱⁱⁱ	0.89	2.02	2.785 (3)	143

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

Acknowledgements

The author thanks Southeast University for financial support of this research and is grateful for the guidance of Professor Wen Zhang.

References

Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
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