4-Ethyl­anilinium 4-methyl­benzene­sulfonate

Wu, D.-H.; Wu, Q.-Q.

doi:10.1107/S1600536810028047

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2065

https://doi.org/10.1107/S1600536810028047

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4-Ethylanilinium 4-methylbenzenesulfonate

De-Hong Wu ^a ^* and Qi-Qi Wu ^a

^aCollege of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: wudh1971@sohu.com

(Received 12 July 2010; accepted 14 July 2010; online 21 July 2010)

In the crystal structure of the title molecular salt, C₈H₁₂N⁺·C₇H₇O₃S⁻, the 4-ethylanilinium cations and 4-methylbenzenesulfonate anions are linked into chains parallel to the b axis by intermolecular N—H⋯O hydrogen bonds.

Related literature

For background literature concerning molecular–ionic compounds, see: Czupiński et al. (2002 ); Katrusiak & Szafrański (2006 ). For related structures. see: Chen (2009 ); Wang (2010 ).

Experimental

Crystal data

C₈H₁₂N⁺·C₇H₇O₃S⁻
M_r = 293.38
Monoclinic, C 2/c
a = 25.016 (3) Å
b = 5.6376 (11) Å
c = 21.6387 (13) Å
β = 95.227 (10)°
V = 3039.0 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 291 K
0.36 × 0.28 × 0.24 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.930, T_max = 0.950
14572 measured reflections
3490 independent reflections
2614 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.178
S = 1.06
3490 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯O1ⁱ	0.89	2.24	2.792 (3)	120
N1—H1D⋯O1	0.89	2.26	3.085 (3)	154
N1—H1E⋯O2ⁱⁱ	0.89	2.04	2.815 (3)	146
N1—H1F⋯O3ⁱⁱⁱ	0.89	2.24	2.808 (3)	122
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) $[-x+1, y-1, -z+{\script{1\over 2}}]$ .

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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810028047/rz2476sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810028047/rz2476Isup2.hkl

checkCIF report

Comment top

Recently much attention has been devoted to simple molecular–ionic crystals containing organic cations and anions due to the tunability of their special structural features and their interesting physical properties (Czupiński et al., 2002; Katrusiak & Szafrański, 2006). For similar structures, see: Chen, 2009; Wang, 2010. In our laboratory, the title compound has been synthesized and its crystal structure is herein reported.

The asymmetric unit of the title compound consists of a 4-ethylanilinium cation and a 4-methylbenzenesulfonate anion (Fig 1), in which proton transfer from the acid to the basic component has occurred (Fig. 1). In the crystal packing (Fig. 2), cations and anions are linked into one-dimensional chains parallel to b-axis by intermolecular N—H···O hydrogen bonds (Table 1).

Related literature top

For background literature concerning molecular–ionic compounds, see: Czupiński et al. (2002); Katrusiak & Szafrański (2006). For related structures. see: Chen (2009); Wang (2010).

Experimental top

4-Methylbenzenesulfonic acid hydrate (1.90 g; 10 mmol) was firstly dissolved in 50 ml ethanol, to which 4-ethybenzenamine (1.21 g; 10 mmol) was added under stirring at the ambient temperature to afford a clear solution without any participation. Single crystals suitable for X-ray structure analysis were obtained by slow evaporation of the above solution after 5 days in air (m. p. 192 °C).

The dielectric constant of the compound as a function of temperature indicates that the permittivity is basically temperature-independent (ε = C/(T–T₀)), suggesting that this compound is not ferroelectric or there may be no distinct phase transition occurring within the measured temperature range between 93 K and 455 K.

Structure description top

For background literature concerning molecular–ionic compounds, see: Czupiński et al. (2002); Katrusiak & Szafrański (2006). For related structures. see: Chen (2009); Wang (2010).

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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme with 30% probability displacement ellipsoids.
	Fig. 2. Crystal packing of the title compound viewed along the a axis. Hydrogen atoms not involved in hydrogen bonds (dashed lines) are omitted for clarity.

4-Ethylanilinium 4-methylbenzenesulfonate top

Crystal data top

C₈H₁₂N⁺·C₇H₇O₃S⁻	F(000) = 1248
M_r = 293.38	D_x = 1.283 Mg m⁻³
Monoclinic, C2/c	Melting point: 465 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 25.016 (3) Å	Cell parameters from 12307 reflections
b = 5.6376 (11) Å	θ = 3.1–27.6°
c = 21.6387 (13) Å	µ = 0.22 mm⁻¹
β = 95.227 (10)°	T = 291 K
V = 3039.0 (7) Å³	Block, colourless
Z = 8	0.36 × 0.28 × 0.24 mm

Data collection top

Rigaku Mercury2 diffractometer	3490 independent reflections
Radiation source: fine-focus sealed tube	2614 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
CCD_Profile_fitting scans	h = −32→32
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −7→7
T_min = 0.930, T_max = 0.950	l = −27→28
14572 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0988P)² + 1.990P] where P = (F_o² + 2F_c²)/3
3490 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₈H₁₂N⁺·C₇H₇O₃S⁻	V = 3039.0 (7) Å³
M_r = 293.38	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 25.016 (3) Å	µ = 0.22 mm⁻¹
b = 5.6376 (11) Å	T = 291 K
c = 21.6387 (13) Å	0.36 × 0.28 × 0.24 mm
β = 95.227 (10)°

Data collection top

Rigaku Mercury2 diffractometer	3490 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2614 reflections with I > 2σ(I)
T_min = 0.930, T_max = 0.950	R_int = 0.048
14572 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.178	H-atom parameters constrained
S = 1.06	Δρ_max = 0.41 e Å⁻³
3490 reflections	Δρ_min = −0.44 e Å⁻³
181 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
C1	0.18002 (12)	0.6568 (8)	0.1475 (2)	0.0771 (11)
H1A	0.1636	0.7869	0.1243	0.116*
H1B	0.1634	0.6386	0.1855	0.116*
H1C	0.1754	0.5138	0.1235	0.116*
C2	0.23944 (10)	0.7059 (5)	0.16208 (13)	0.0448 (7)
C3	0.26270 (11)	0.9123 (6)	0.14269 (15)	0.0549 (8)
H3A	0.2414	1.0231	0.1201	0.066*
C4	0.31647 (11)	0.9576 (5)	0.15593 (14)	0.0471 (7)
H4A	0.3311	1.0985	0.1428	0.056*
C5	0.34871 (9)	0.7941 (4)	0.18873 (10)	0.0304 (5)
C6	0.32643 (10)	0.5882 (5)	0.20886 (13)	0.0416 (6)
H6A	0.3478	0.4769	0.2312	0.050*
C7	0.27173 (11)	0.5477 (5)	0.19556 (13)	0.0473 (7)
H7A	0.2568	0.4094	0.2098	0.057*
C8	0.32058 (15)	0.5450 (11)	0.52795 (18)	0.1058 (18)
H8A	0.3026	0.5895	0.5635	0.159*
H8B	0.3130	0.3819	0.5180	0.159*
H8C	0.3082	0.6432	0.4933	0.159*
C9	0.37861 (13)	0.5763 (7)	0.54173 (14)	0.0620 (9)
H9A	0.3908	0.4785	0.5771	0.074*
H9B	0.3859	0.7404	0.5530	0.074*
C10	0.41024 (10)	0.5113 (5)	0.48754 (12)	0.0414 (6)
C11	0.41036 (12)	0.6573 (5)	0.43615 (13)	0.0473 (7)
H11A	0.3919	0.8006	0.4358	0.057*
C12	0.43700 (11)	0.5966 (5)	0.38534 (12)	0.0420 (6)
H12A	0.4365	0.6969	0.3512	0.050*
C13	0.46425 (9)	0.3857 (4)	0.38629 (11)	0.0317 (5)
C14	0.46589 (10)	0.2380 (5)	0.43700 (12)	0.0417 (6)
H14A	0.4851	0.0967	0.4375	0.050*
C15	0.43868 (11)	0.3020 (5)	0.48717 (13)	0.0467 (7)
H15A	0.4396	0.2019	0.5214	0.056*
N1	0.49149 (8)	0.3138 (4)	0.33224 (9)	0.0373 (5)
H1D	0.4874	0.4261	0.3033	0.056*
H1E	0.4774	0.1786	0.3171	0.056*
H1F	0.5263	0.2931	0.3435	0.056*
O1	0.44138 (7)	0.6248 (4)	0.22484 (10)	0.0543 (6)
O2	0.42345 (8)	1.0277 (4)	0.25272 (9)	0.0534 (5)
O3	0.43719 (8)	0.9314 (4)	0.14712 (9)	0.0575 (6)
S1	0.41818 (2)	0.84917 (11)	0.20463 (3)	0.0335 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0355 (16)	0.105 (3)	0.089 (3)	−0.0119 (18)	−0.0011 (16)	−0.011 (2)
C2	0.0313 (13)	0.0591 (18)	0.0439 (14)	−0.0054 (12)	0.0019 (11)	−0.0108 (13)
C3	0.0425 (15)	0.0547 (18)	0.0650 (19)	0.0104 (13)	−0.0090 (14)	0.0114 (16)
C4	0.0420 (14)	0.0369 (14)	0.0616 (18)	−0.0030 (12)	0.0007 (12)	0.0127 (13)
C5	0.0289 (11)	0.0313 (12)	0.0311 (11)	−0.0021 (9)	0.0031 (9)	−0.0010 (9)
C6	0.0387 (13)	0.0366 (14)	0.0486 (15)	−0.0047 (11)	−0.0004 (11)	0.0118 (12)
C7	0.0450 (15)	0.0435 (16)	0.0543 (16)	−0.0164 (13)	0.0093 (12)	0.0019 (13)
C8	0.068 (2)	0.188 (5)	0.067 (2)	−0.008 (3)	0.032 (2)	−0.023 (3)
C9	0.069 (2)	0.076 (2)	0.0434 (16)	0.0024 (18)	0.0176 (15)	−0.0095 (17)
C10	0.0435 (14)	0.0475 (15)	0.0338 (13)	−0.0005 (12)	0.0067 (11)	−0.0056 (12)
C11	0.0578 (17)	0.0398 (15)	0.0454 (15)	0.0134 (13)	0.0117 (13)	−0.0001 (12)
C12	0.0542 (16)	0.0352 (14)	0.0373 (14)	0.0034 (12)	0.0084 (11)	0.0060 (11)
C13	0.0303 (11)	0.0342 (13)	0.0308 (12)	−0.0043 (10)	0.0037 (9)	−0.0019 (10)
C14	0.0441 (14)	0.0363 (14)	0.0449 (15)	0.0076 (12)	0.0045 (12)	0.0071 (12)
C15	0.0531 (16)	0.0511 (17)	0.0360 (14)	0.0065 (13)	0.0055 (12)	0.0122 (12)
N1	0.0373 (11)	0.0397 (12)	0.0355 (11)	−0.0024 (9)	0.0067 (8)	−0.0065 (9)
O1	0.0368 (10)	0.0510 (12)	0.0746 (15)	0.0090 (9)	0.0017 (9)	0.0067 (11)
O2	0.0467 (11)	0.0567 (13)	0.0561 (12)	−0.0120 (9)	0.0005 (9)	−0.0235 (10)
O3	0.0493 (12)	0.0805 (16)	0.0439 (11)	−0.0235 (11)	0.0106 (9)	0.0028 (11)
S1	0.0288 (3)	0.0368 (4)	0.0350 (3)	−0.0045 (2)	0.0031 (2)	−0.0028 (3)

Geometric parameters (Å, º) top

C1—C2	1.517 (4)	C9—H9A	0.9700
C1—H1A	0.9600	C9—H9B	0.9700
C1—H1B	0.9600	C10—C15	1.378 (4)
C1—H1C	0.9600	C10—C11	1.384 (4)
C2—C7	1.366 (4)	C11—C12	1.379 (4)
C2—C3	1.383 (4)	C11—H11A	0.9300
C3—C4	1.374 (4)	C12—C13	1.370 (3)
C3—H3A	0.9300	C12—H12A	0.9300
C4—C5	1.378 (3)	C13—C14	1.375 (3)
C4—H4A	0.9300	C13—N1	1.463 (3)
C5—C6	1.375 (3)	C14—C15	1.381 (4)
C5—S1	1.768 (2)	C14—H14A	0.9300
C6—C7	1.391 (4)	C15—H15A	0.9300
C6—H6A	0.9300	N1—H1D	0.8900
C7—H7A	0.9300	N1—H1E	0.8900
C8—C9	1.466 (5)	N1—H1F	0.8900
C8—H8A	0.9600	O1—S1	1.443 (2)
C8—H8B	0.9600	O2—S1	1.4451 (19)
C8—H8C	0.9600	O3—S1	1.448 (2)
C9—C10	1.518 (4)

C2—C1—H1A	109.5	C8—C9—H9B	109.0
C2—C1—H1B	109.5	C10—C9—H9B	109.0
H1A—C1—H1B	109.5	H9A—C9—H9B	107.8
C2—C1—H1C	109.5	C15—C10—C11	117.7 (2)
H1A—C1—H1C	109.5	C15—C10—C9	121.1 (3)
H1B—C1—H1C	109.5	C11—C10—C9	121.1 (3)
C7—C2—C3	117.7 (2)	C12—C11—C10	122.0 (2)
C7—C2—C1	120.8 (3)	C12—C11—H11A	119.0
C3—C2—C1	121.5 (3)	C10—C11—H11A	119.0
C4—C3—C2	121.6 (3)	C13—C12—C11	118.6 (2)
C4—C3—H3A	119.2	C13—C12—H12A	120.7
C2—C3—H3A	119.2	C11—C12—H12A	120.7
C3—C4—C5	119.9 (3)	C12—C13—C14	121.1 (2)
C3—C4—H4A	120.0	C12—C13—N1	119.7 (2)
C5—C4—H4A	120.0	C14—C13—N1	119.2 (2)
C6—C5—C4	119.5 (2)	C13—C14—C15	119.2 (2)
C6—C5—S1	120.41 (19)	C13—C14—H14A	120.4
C4—C5—S1	120.08 (19)	C15—C14—H14A	120.4
C5—C6—C7	119.5 (2)	C10—C15—C14	121.3 (2)
C5—C6—H6A	120.2	C10—C15—H15A	119.3
C7—C6—H6A	120.2	C14—C15—H15A	119.3
C2—C7—C6	121.7 (3)	C13—N1—H1D	109.5
C2—C7—H7A	119.2	C13—N1—H1E	109.5
C6—C7—H7A	119.2	H1D—N1—H1E	109.5
C9—C8—H8A	109.5	C13—N1—H1F	109.5
C9—C8—H8B	109.5	H1D—N1—H1F	109.5
H8A—C8—H8B	109.5	H1E—N1—H1F	109.5
C9—C8—H8C	109.5	O1—S1—O2	112.62 (13)
H8A—C8—H8C	109.5	O1—S1—O3	112.74 (14)
H8B—C8—H8C	109.5	O2—S1—O3	112.34 (13)
C8—C9—C10	113.0 (3)	O1—S1—C5	105.43 (11)
C8—C9—H9A	109.0	O2—S1—C5	106.63 (11)
C10—C9—H9A	109.0	O3—S1—C5	106.43 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···O1ⁱ	0.89	2.24	2.792 (3)	120
N1—H1D···O1	0.89	2.26	3.085 (3)	154
N1—H1E···O2ⁱⁱ	0.89	2.04	2.815 (3)	146
N1—H1F···O3ⁱⁱⁱ	0.89	2.24	2.808 (3)	122

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

Experimental details

Crystal data
Chemical formula	C₈H₁₂N⁺·C₇H₇O₃S⁻
M_r	293.38
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	291
a, b, c (Å)	25.016 (3), 5.6376 (11), 21.6387 (13)
β (°)	95.227 (10)
V (Å³)	3039.0 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.36 × 0.28 × 0.24

Data collection
Diffractometer	Rigaku Mercury2
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.930, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	14572, 3490, 2614
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.178, 1.06
No. of reflections	3490
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.44

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···O1ⁱ	0.89	2.24	2.792 (3)	120.2
N1—H1D···O1	0.89	2.26	3.085 (3)	154.2
N1—H1E···O2ⁱⁱ	0.89	2.04	2.815 (3)	145.7
N1—H1F···O3ⁱⁱⁱ	0.89	2.24	2.808 (3)	121.7

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

Acknowledgements

The authors thank the China Postdoctoral Science Foundation funded project (20090451147), the Jiangsu Planned Projects for Postdoctoral Research Funds (0802003B) and the SEU Major Postdoctoral Research Funds (3212000901) for financial support.

References

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