3-Fluoro-anilinium 4-methyl-benzene-sulfonate.

In the crystal structure of the title salt, C(6)H(7)FN(+)·C(7)H(7)O(3)S(-), the components are linked into chains along [010] via N-H⋯O hydrogen bonds. Further stabilization is is provided by weak π-π stacking inter-actions, 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 = 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

Δρmax = 0.34 e Å−3

Δρmin = −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.

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

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

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

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

C6H7FN+·C7H7O3S−	F(000) = 592
Mr = 283.31	Dx = 1.370 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 2843 reflections
a = 14.5385 (7) Å	θ = 4.2–71.3°
b = 6.4939 (3) Å	µ = 2.25 mm−1
c = 14.5522 (7) Å	T = 173 K
β = 91.429 (4)°	Rod, colorless
V = 1373.47 (11) Å3	0.40 × 0.10 × 0.07 mm
Z = 4

Oxford Diffraction Xcalibur Eos Gemini diffractometer	2642 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2076 reflections with I > 2σ(I)
graphite	Rint = 0.030
Detector resolution: 16.1500 pixels mm-1	θmax = 71.5°, θmin = 4.3°
ω scans	h = −17→17
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −7→7
Tmin = 0.466, Tmax = 0.858	l = −13→17
8663 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0665P)2 + 0.2763P] where P = (Fo2 + 2Fc2)/3
2642 reflections	(Δ/σ)max < 0.001
174 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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.

	x	y	z	Uiso*/Ueq
S1	0.84338 (3)	0.25122 (6)	0.46398 (3)	0.03256 (17)
F1	0.93374 (13)	1.1392 (2)	0.84280 (10)	0.0794 (5)
O1	0.79440 (10)	0.0607 (2)	0.48237 (9)	0.0439 (4)
O2	0.79079 (9)	0.4330 (2)	0.48854 (9)	0.0412 (3)
O3	0.93526 (10)	0.2539 (2)	0.50709 (9)	0.0416 (3)
N1	0.88997 (11)	0.7501 (2)	0.56685 (11)	0.0366 (4)
H1NC	0.8610	0.6332	0.5475	0.044*
H1NB	0.9504	0.7439	0.5524	0.044*
H1NA	0.8634	0.8611	0.5387	0.044*
C1	0.85900 (13)	0.2623 (3)	0.34404 (12)	0.0338 (4)
C2	0.83246 (14)	0.1018 (4)	0.28787 (14)	0.0462 (5)
H2A	0.8042	−0.0165	0.3132	0.055*
C3	0.84700 (15)	0.1129 (4)	0.19455 (15)	0.0559 (6)
H3A	0.8291	0.0007	0.1562	0.067*
C4	0.88712 (14)	0.2840 (4)	0.15601 (14)	0.0527 (6)
C5	0.91260 (15)	0.4458 (4)	0.21321 (15)	0.0510 (6)
H5A	0.9398	0.5652	0.1876	0.061*
C6	0.89915 (14)	0.4368 (3)	0.30711 (14)	0.0439 (5)
H6A	0.9172	0.5485	0.3457	0.053*
C7	0.90233 (19)	0.2933 (5)	0.05369 (16)	0.0751 (9)
H7A	0.8498	0.2305	0.0208	0.113*
H7B	0.9586	0.2180	0.0393	0.113*
H7C	0.9084	0.4372	0.0346	0.113*
C8	0.90357 (16)	0.9645 (3)	0.80119 (15)	0.0486 (5)
C9	0.91293 (14)	0.9489 (3)	0.70742 (13)	0.0410 (5)
H9A	0.9395	1.0566	0.6727	0.049*
C10	0.88200 (13)	0.7699 (3)	0.66649 (13)	0.0349 (4)
C11	0.84357 (14)	0.6132 (3)	0.71594 (14)	0.0461 (5)
H11A	0.8232	0.4906	0.6862	0.055*
C12	0.83496 (15)	0.6368 (4)	0.81015 (15)	0.0529 (6)
H12A	0.8081	0.5297	0.8450	0.064*
C13	0.86476 (15)	0.8130 (4)	0.85343 (14)	0.0506 (5)
H13A	0.8587	0.8299	0.9178	0.061*

	U11	U22	U33	U12	U13	U23
S1	0.0320 (3)	0.0375 (3)	0.0283 (3)	−0.00209 (16)	0.00377 (18)	−0.00070 (17)
F1	0.1225 (14)	0.0660 (10)	0.0500 (8)	−0.0095 (9)	0.0073 (8)	−0.0225 (7)
O1	0.0454 (8)	0.0452 (8)	0.0413 (7)	−0.0080 (6)	0.0032 (6)	0.0051 (6)
O2	0.0413 (8)	0.0467 (8)	0.0359 (7)	0.0036 (6)	0.0064 (6)	−0.0057 (6)
O3	0.0361 (8)	0.0580 (9)	0.0309 (7)	−0.0023 (6)	0.0018 (6)	0.0006 (6)
N1	0.0354 (9)	0.0401 (8)	0.0345 (8)	−0.0007 (6)	0.0065 (7)	−0.0015 (6)
C1	0.0289 (9)	0.0441 (10)	0.0286 (9)	0.0011 (7)	0.0028 (7)	−0.0005 (7)
C2	0.0391 (11)	0.0579 (12)	0.0416 (11)	−0.0123 (9)	0.0038 (9)	−0.0111 (9)
C3	0.0408 (12)	0.0859 (17)	0.0411 (11)	−0.0093 (11)	0.0022 (9)	−0.0214 (11)
C4	0.0326 (11)	0.0932 (18)	0.0324 (11)	0.0096 (11)	0.0018 (9)	−0.0031 (11)
C5	0.0454 (13)	0.0633 (14)	0.0448 (12)	0.0046 (10)	0.0098 (10)	0.0135 (10)
C6	0.0460 (12)	0.0467 (11)	0.0393 (10)	−0.0014 (9)	0.0062 (9)	0.0007 (9)
C7	0.0528 (15)	0.139 (3)	0.0339 (12)	0.0110 (16)	0.0056 (11)	0.0037 (14)
C8	0.0513 (13)	0.0533 (12)	0.0415 (11)	0.0046 (10)	0.0039 (9)	−0.0089 (9)
C9	0.0455 (12)	0.0405 (10)	0.0375 (10)	0.0011 (8)	0.0073 (8)	−0.0006 (8)
C10	0.0283 (9)	0.0433 (10)	0.0334 (9)	0.0024 (7)	0.0067 (7)	0.0001 (7)
C11	0.0401 (11)	0.0542 (12)	0.0440 (11)	−0.0093 (9)	0.0037 (9)	0.0036 (9)
C12	0.0404 (12)	0.0742 (16)	0.0447 (12)	−0.0089 (11)	0.0100 (9)	0.0139 (11)
C13	0.0400 (11)	0.0786 (15)	0.0338 (10)	0.0085 (11)	0.0091 (9)	0.0028 (10)

S1—O1	1.4555 (14)	C5—C6	1.386 (3)
S1—O2	1.4561 (14)	C5—H5A	0.9500
S1—O3	1.4615 (15)	C6—H6A	0.9500
S1—C1	1.7671 (18)	C7—H7A	0.9800
F1—C8	1.354 (3)	C7—H7B	0.9800
N1—C10	1.463 (2)	C7—H7C	0.9800
N1—H1NC	0.9100	C8—C13	1.373 (3)
N1—H1NB	0.9100	C8—C9	1.378 (3)
N1—H1NA	0.9100	C9—C10	1.376 (3)
C1—C2	1.374 (3)	C9—H9A	0.9500
C1—C6	1.389 (3)	C10—C11	1.373 (3)
C2—C3	1.381 (3)	C11—C12	1.388 (3)
C2—H2A	0.9500	C11—H11A	0.9500
C3—C4	1.381 (3)	C12—C13	1.371 (3)
C3—H3A	0.9500	C12—H12A	0.9500
C4—C5	1.385 (3)	C13—H13A	0.9500
C4—C7	1.512 (3)
O1—S1—O2	112.44 (8)	C5—C6—C1	119.1 (2)
O1—S1—O3	112.18 (8)	C5—C6—H6A	120.4
O2—S1—O3	111.39 (8)	C1—C6—H6A	120.4
O1—S1—C1	106.95 (8)	C4—C7—H7A	109.5
O2—S1—C1	106.89 (8)	C4—C7—H7B	109.5
O3—S1—C1	106.56 (8)	H7A—C7—H7B	109.5
C10—N1—H1NC	109.5	C4—C7—H7C	109.5
C10—N1—H1NB	109.5	H7A—C7—H7C	109.5
H1NC—N1—H1NB	109.5	H7B—C7—H7C	109.5
C10—N1—H1NA	109.5	F1—C8—C13	119.1 (2)
H1NC—N1—H1NA	109.5	F1—C8—C9	117.7 (2)
H1NB—N1—H1NA	109.5	C13—C8—C9	123.2 (2)
C2—C1—C6	120.20 (18)	C10—C9—C8	116.80 (19)
C2—C1—S1	121.05 (15)	C10—C9—H9A	121.6
C6—C1—S1	118.74 (14)	C8—C9—H9A	121.6
C1—C2—C3	119.9 (2)	C11—C10—C9	122.15 (19)
C1—C2—H2A	120.1	C11—C10—N1	119.83 (17)
C3—C2—H2A	120.1	C9—C10—N1	118.02 (16)
C4—C3—C2	121.2 (2)	C10—C11—C12	118.9 (2)
C4—C3—H3A	119.4	C10—C11—H11A	120.5
C2—C3—H3A	119.4	C12—C11—H11A	120.5
C3—C4—C5	118.42 (19)	C13—C12—C11	120.7 (2)
C3—C4—C7	120.4 (2)	C13—C12—H12A	119.7
C5—C4—C7	121.2 (2)	C11—C12—H12A	119.7
C4—C5—C6	121.2 (2)	C12—C13—C8	118.23 (19)
C4—C5—H5A	119.4	C12—C13—H13A	120.9
C6—C5—H5A	119.4	C8—C13—H13A	120.9
O1—S1—C1—C2	−4.3 (2)	C4—C5—C6—C1	−0.3 (3)
O2—S1—C1—C2	−124.97 (17)	C2—C1—C6—C5	−0.5 (3)
O3—S1—C1—C2	115.82 (18)	S1—C1—C6—C5	179.29 (16)
O1—S1—C1—C6	175.90 (15)	F1—C8—C9—C10	179.88 (19)
O2—S1—C1—C6	55.27 (17)	C13—C8—C9—C10	−0.7 (3)
O3—S1—C1—C6	−63.94 (17)	C8—C9—C10—C11	0.0 (3)
C6—C1—C2—C3	1.0 (3)	C8—C9—C10—N1	179.24 (17)
S1—C1—C2—C3	−178.81 (17)	C9—C10—C11—C12	0.5 (3)
C1—C2—C3—C4	−0.7 (4)	N1—C10—C11—C12	−178.71 (18)
C2—C3—C4—C5	−0.1 (3)	C10—C11—C12—C13	−0.4 (3)
C2—C3—C4—C7	−179.9 (2)	C11—C12—C13—C8	−0.3 (3)
C3—C4—C5—C6	0.6 (3)	F1—C8—C13—C12	−179.7 (2)
C7—C4—C5—C6	−179.6 (2)	C9—C8—C13—C12	0.8 (3)

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.

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

Symmetry codes: (i) ; (ii) .