3-Fluoro­anilinium 4-methyl­benzene­sulfonate

Jerry P Jasinski; James A Golen; A S Praveen; H S Yathirajan; B Narayana

doi:10.1107/S1600536811041055

. 2011 Oct 12;67(Pt 11):o2924. doi: 10.1107/S1600536811041055

3-Fluoroanilinium 4-methylbenzenesulfonate

Jerry P Jasinski ^a,^*, James A Golen ^a, A S Praveen ^b, H S Yathirajan ^b, B Narayana ^c

PMCID: PMC3247338 PMID: 22219956

Abstract

In the crystal structure of the title salt, C₆H₇FN⁺·C₇H₇O₃S⁻, the components are linked into chains along [010] via N—H⋯O hydrogen bonds. Further stabilization is is provided by weak π–π stacking interactions, with a centroid–centroid distance of 3.7156 (12) Å.

Related literature

For molecular salts as solid forms in pharmaceutical formulations, see: Stahl & Wermuth (2002 ▶). For related structures, see: Chanawanno et al. (2009 ▶); Chantrapromma et al. (2010 ▶); Collier et al. (2006 ▶); Fun et al. (2010 ▶); Li et al. (2005 ▶); Lin (2010 ▶); Tabatabaee & Noozari (2011 ▶); Wu et al. (2009 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₆H₇FN⁺·C₇H₇O₃S⁻
M _r = 283.31
Monoclinic,
a = 14.5385 (7) Å
b = 6.4939 (3) Å
c = 14.5522 (7) Å
β = 91.429 (4)°
V = 1373.47 (11) Å³
Z = 4
Cu Kα radiation
μ = 2.25 mm⁻¹
T = 173 K
0.40 × 0.10 × 0.07 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T _min = 0.466, T _max = 0.858
8663 measured reflections
2642 independent reflections
2076 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.121
S = 1.05
2642 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); 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.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811041055/lh5330sup1.cif

e-67-o2924-sup1.cif^{(22.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811041055/lh5330Isup2.hkl

e-67-o2924-Isup2.hkl^{(129.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811041055/lh5330Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1NB⋯O3ⁱ	0.91	1.89	2.784 (2)	166
N1—H1NA⋯O1ⁱⁱ	0.91	1.82	2.725 (2)	171
N1—H1NC⋯O2	0.91	1.85	2.745 (2)	167

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

ASP and HSY thank the UoM for research facilities. JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

Comment

The importance of molecular salts as solid forms in pharmaceutical formulations is well known (Stahl & Wermuth, 2002). A variety of pharmaceutical drugs are prepared as salts of benzenesulfonic acid and are known as besylates. Benzenesulfonic acid is also used as an acidic catalyst in esterification and dehydration reactions. In the title compound, the proton of the sulfonic group of sulfonic acid has been transferred to the N atom of the 3-fluoroaniline molecule, leading to the formation of the molecular complex, (I). Crystal structures of some benzenesulfonate derivatives, viz., 2,4,6-triamino-1,3,5-triazin-1-ium 4-methylbenzenesulfonate monohydrate (Li et al., 2005), ephedrine besylate (Collier et al., 2006), 2-ethyl-6-methylanilinium 4-methylbenzenesulfonate (Wu et al., 2009), 2-[(E)-2-(4-ethoxyphenyl)ethenyl]-1-methylpyridinium 4-methylbenzenesulfonate monohydrate (Chanawanno et al., 2009), 2-aminopyrimidin-1-ium 4-methylbenzenesulfonate (Tabatabaee & Noozari, 2011), 4-(cyanomethyl)anilinium 4-methylbenzenesulfonate monohydrate (Lin, 2010), 1-methyl-2-[(E)-2-(2-thienyl)etheny] quinolinium 4-bromobenzenesulfonate (Fun et al., 2010) and (E)-2-[4-(dimethylamino)styryl]-1-methylpyridinium 4-methylbenzenesulfonate monohydrate (Chantrapromma et al., 2010) have been reported. In view of the importance of benzenesulphonic acid, we report herein the crystal structure of the title compound (I).

In the crystal structure of the title salt, C₆H₇FN⁺, C₇H₇O₃S^-, (Fig. 1) N—H···O hydrogen bonds link the components into one-dimensional chains along [010] (Fig. 2). Further stabilization is is provided by weak π–π stacking interactions with a centroid to centroid distance of 3.7156 (12)Å.

Experimental

4-methylbenzenesulfonic acid monohydrate (1 g, 5.25 mmol) was added to a stirred solution of 3-fluoroaniline (0.58 g, 5.25 mmol ) in methanol (10 mL). Resulting mixture was stirred at 323 K for 10 minutes and cooled to room temperature to obtain the title compound (I), Fig. 1. The single crystal was grown from methanol by slow evaporation method (m.p.: 533 K).