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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1797.
Published online 2009 July 8. doi:  10.1107/S1600536809025835
PMCID: PMC2977346

Pyridinium 4-(trifluoro­meth­yl)benzene­sulfonate

Abstract

The title salt, C5H6N+·C7H4F3O3S, is an ion pair in which the pyridium cation is linked to the 4-(trifluoro­meth­yl)benzene­sulfonate anion by an N—H(...)O hydrogen bond. The F atoms of the trifluoro­methyl group are disordered over two sites in a 0.584 (9):0.416 (9) ratio.

Related literature

For the use of 4-(trifluoro­meth­yl)benzene­sulfonate anion as a rust inhibitor, see: Otomo (1993 [triangle]). For comparative bond dimensions for the anion, see: Bats et al. (1999 [triangle]); Bernhard et al. (1982 [triangle]); Kozioł & Podkowińska (1983 [triangle]), and for the cation, see: Djinović & Golič (1992 [triangle]) (1992); Ziemer & Rabis (2000 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1797-scheme1.jpg

Experimental

Crystal data

  • C5H6N+·C7H4F3O3S
  • M r = 305.27
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1797-efi1.jpg
  • a = 5.7905 (5) Å
  • b = 9.0294 (7) Å
  • c = 24.988 (2) Å
  • β = 90.8220 (10)°
  • V = 1306.35 (18) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.29 mm−1
  • T = 273 K
  • 0.49 × 0.35 × 0.25 mm

Data collection

  • Bruker SMART APEX area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.871, T max = 0.931
  • 6394 measured reflections
  • 2291 independent reflections
  • 1880 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.088
  • wR(F 2) = 0.242
  • S = 1.07
  • 2291 reflections
  • 179 parameters
  • 15 restraints
  • H-atom parameters constrained
  • Δρmax = 0.70 e Å−3
  • Δρmin = −0.53 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809025835/ng2593sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025835/ng2593Isup2.hkl

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

supplementary crystallographic information

Comment

4-(Trifluoromethyl)benzenesulfonate was considered as excellent organic rust inhibitors which can effectively prevent corrosion of metals such as steel, copper, manganese and nickel (Otomo et al., 1993). In our laboratory, a new compound containing 4-(trifluoromethyl)benzenesulfonate, (I), has been synthesized, its structure is studied hereafter.

Fig. 1 presents a view of the asymmetric unit: one pyridium cation and one 4-(trifluoromethyl)benzenesulfonate anion. In the anion the average C—C bond distance in the ring, 1.372 Å, is consistent with the value usually accepted. The internal angle (C4—C5—C6) is decreased to 118.0 (5)°, and endocyclic angle of C3—C2—C7 to 118.3 (5)°. The S—C distance of 1.795 (5)Å is close to the experimental values of 1.77 (Bats et al., 1999), 1.766 (Bernhard et al., 1982) and 1.782 (Kozioł & Podlowińska, 1983). The phenyl ring and the S atom are almost planar, which is displaced from the mean plane of the phenyl ring by 0.010 (6) Å. Three F atom in the trifluoromethyl group is disorder.

In the cation, distances in the pyridinium ring are in the range 1.319 (7)–1.372 (8)Å and angles 118.6 (5)–122.0 (5)°, which are similar to those found in research of Djinović & Golič (1992) and Ziemer et al. (2000).

The ion pairs are formed via a N1—H1···O3 hydrogen bond (Fig. 2). In addition, week C—H···O hydrogen bonds stabilize the crystal (Fig. 2 & Table 2).

Experimental

4-(Trifluoromethyl)benzenesulfonic acid and pyridine in a molar ratio of 1:1 were mixed and dissolved in sufficient ethanol by heating to 365 K, when a clear solution resulted. Crystals of (I) were formed by gradual evaporation of excess ethanol over a period of one week at 293 K.

Refinement

All of the H atoms were placed in calculated positions and allowed to ride on their parent atoms at distances of 0.86 (N—H), 0.93Å (aromatic), with Uiso(H) = 1.2–1.5 Ueq(C, N). Three disordered F atoms were split into approximately halves, with occupancies of 0.584 (9) and 0.416 (9). All the C—F distances are restrained to be identical with deviation of 0.01 Å.

Figures

Fig. 1.
The cell unit of (I) with atom labels, showing 30% probability displacement ellipsoids. Parts of disorder F atoms was deleted for clarity.
Fig. 2.
A packing diagram viewed down along the a axis. Hydrogen bonds are illustrated as thin lines. Parts of disorder F atoms was deleted for clarity.

Crystal data

C5H6N+·C7H4F3O3SF(000) = 624
Mr = 305.27Dx = 1.552 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2733 reflections
a = 5.7905 (5) Åθ = 2.4–25.0°
b = 9.0294 (7) ŵ = 0.29 mm1
c = 24.988 (2) ÅT = 273 K
β = 90.822 (1)°Prism, colorless
V = 1306.35 (18) Å30.49 × 0.35 × 0.25 mm
Z = 4

Data collection

Bruker APEX area-detector diffractometer2291 independent reflections
Radiation source: fine-focus sealed tube1880 reflections with I > 2σ(I)
graphiteRint = 0.031
[var phi] and ω scansθmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −6→6
Tmin = 0.871, Tmax = 0.931k = −10→10
6394 measured reflectionsl = −22→29

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.088Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.242H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.1117P)2 + 3.3401P] where P = (Fo2 + 2Fc2)/3
2291 reflections(Δ/σ)max = 0.001
179 parametersΔρmax = 0.70 e Å3
15 restraintsΔρmin = −0.53 e Å3

Special details

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)

xyzUiso*/UeqOcc. (<1)
S11.1078 (2)0.88952 (12)0.32068 (5)0.0451 (4)
O11.3546 (6)0.8891 (4)0.32268 (15)0.0603 (10)
O21.0094 (6)1.0326 (4)0.30758 (14)0.0595 (10)
O31.0162 (7)0.7709 (4)0.28780 (15)0.0629 (10)
C10.7591 (12)0.7361 (7)0.5413 (3)0.086 (2)
C20.8504 (10)0.7742 (7)0.4880 (2)0.0598 (14)
C30.7200 (11)0.8601 (8)0.4550 (3)0.0756 (18)
H30.57800.89540.46640.091*
C40.7974 (10)0.8958 (7)0.4043 (2)0.0679 (16)
H40.70500.95350.38180.082*
C51.0090 (8)0.8472 (5)0.38668 (19)0.0444 (11)
C61.1354 (10)0.7576 (8)0.4195 (2)0.0730 (18)
H61.27610.72030.40800.088*
C71.0565 (12)0.7217 (8)0.4696 (3)0.081 (2)
H71.14550.66020.49150.098*
F1'0.9025 (16)0.6547 (13)0.5717 (3)0.1146 (16)0.584 (9)
F2'0.5792 (17)0.6419 (11)0.5388 (4)0.1146 (16)0.584 (9)
F3'0.700 (2)0.8521 (9)0.5715 (3)0.1146 (16)0.584 (9)
F10.921 (2)0.7454 (19)0.5793 (4)0.1146 (16)0.416 (9)
F20.672 (3)0.5995 (12)0.5458 (5)0.1146 (16)0.416 (9)
F30.577 (2)0.8166 (15)0.5579 (5)0.1146 (16)0.416 (9)
N10.6745 (8)0.8321 (6)0.21165 (18)0.0650 (13)
H10.79230.79230.22730.078*
C80.6591 (10)0.9796 (7)0.2096 (2)0.0610 (15)
H80.77541.03760.22480.073*
C90.4777 (10)1.0437 (6)0.1859 (2)0.0613 (14)
H90.46661.14640.18400.074*
C100.3107 (10)0.9570 (7)0.1649 (2)0.0628 (14)
H100.18211.00010.14850.075*
C110.3284 (10)0.8056 (6)0.1673 (2)0.0619 (14)
H110.21200.74590.15310.074*
C120.5144 (10)0.7456 (6)0.1903 (2)0.0581 (14)
H120.53140.64320.19140.070*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0535 (8)0.0315 (6)0.0502 (7)0.0055 (5)−0.0052 (5)0.0001 (5)
O10.057 (2)0.053 (2)0.071 (2)0.0031 (17)−0.0003 (17)0.0060 (17)
O20.074 (3)0.039 (2)0.065 (2)0.0168 (17)−0.0059 (18)0.0063 (16)
O30.086 (3)0.044 (2)0.058 (2)−0.0024 (18)−0.0059 (18)−0.0113 (16)
C10.108 (6)0.083 (5)0.068 (4)0.014 (4)0.002 (4)0.004 (4)
C20.064 (3)0.061 (3)0.055 (3)0.000 (3)−0.003 (2)0.003 (3)
C30.067 (4)0.086 (5)0.074 (4)0.025 (3)0.014 (3)0.013 (3)
C40.061 (3)0.077 (4)0.066 (3)0.023 (3)−0.006 (3)0.015 (3)
C50.048 (3)0.030 (2)0.054 (3)0.004 (2)−0.009 (2)−0.0026 (19)
C60.058 (3)0.093 (5)0.068 (4)0.031 (3)0.001 (3)0.018 (3)
C70.079 (4)0.096 (5)0.068 (4)0.031 (4)−0.008 (3)0.029 (4)
F1'0.145 (4)0.125 (4)0.074 (2)−0.006 (3)0.011 (2)0.022 (2)
F2'0.145 (4)0.125 (4)0.074 (2)−0.006 (3)0.011 (2)0.022 (2)
F3'0.145 (4)0.125 (4)0.074 (2)−0.006 (3)0.011 (2)0.022 (2)
F10.145 (4)0.125 (4)0.074 (2)−0.006 (3)0.011 (2)0.022 (2)
F20.145 (4)0.125 (4)0.074 (2)−0.006 (3)0.011 (2)0.022 (2)
F30.145 (4)0.125 (4)0.074 (2)−0.006 (3)0.011 (2)0.022 (2)
N10.061 (3)0.078 (3)0.057 (3)0.011 (3)−0.002 (2)0.013 (2)
C80.058 (3)0.063 (4)0.062 (3)−0.025 (3)−0.001 (2)−0.008 (3)
C90.079 (4)0.032 (3)0.073 (4)−0.006 (3)0.012 (3)0.000 (2)
C100.055 (3)0.059 (3)0.074 (4)0.006 (3)−0.002 (3)0.010 (3)
C110.066 (4)0.053 (3)0.066 (3)−0.018 (3)−0.004 (3)−0.003 (3)
C120.079 (4)0.032 (3)0.064 (3)0.001 (2)0.007 (3)0.001 (2)

Geometric parameters (Å, °)

S1—O11.429 (4)C5—C61.358 (7)
S1—O31.446 (4)C6—C71.378 (9)
S1—O21.447 (3)C6—H60.9300
S1—C51.795 (5)C7—H70.9300
C1—F11.330 (8)N1—C121.319 (7)
C1—F21.337 (8)N1—C81.336 (8)
C1—F1'1.338 (7)N1—H10.8600
C1—F3'1.339 (7)C8—C91.331 (8)
C1—F2'1.345 (7)C8—H80.9300
C1—F31.353 (8)C9—C101.346 (8)
C1—C21.479 (9)C9—H90.9300
C2—C31.354 (8)C10—C111.372 (8)
C2—C71.370 (9)C10—H100.9300
C3—C41.388 (8)C11—C121.329 (8)
C3—H30.9300C11—H110.9300
C4—C51.379 (7)C12—H120.9300
C4—H40.9300
O1—S1—O3112.1 (2)C6—C5—C4118.0 (5)
O1—S1—O2113.6 (2)C6—C5—S1120.3 (4)
O3—S1—O2113.1 (2)C4—C5—S1121.5 (4)
O1—S1—C5107.4 (2)C5—C6—C7120.4 (5)
O3—S1—C5104.2 (2)C5—C6—H6119.8
O2—S1—C5105.6 (2)C7—C6—H6119.8
F1—C1—F2105.1 (9)C2—C7—C6121.7 (5)
F1'—C1—F3'105.7 (7)C2—C7—H7119.1
F1—C1—F2'127.7 (9)C6—C7—H7119.1
F1'—C1—F2'98.8 (7)C12—N1—C8122.0 (5)
F3'—C1—F2'108.6 (8)C12—N1—H1119.0
F1—C1—F3107.1 (9)C8—N1—H1119.0
F2—C1—F3100.0 (10)C9—C8—N1120.2 (5)
F1—C1—C2111.7 (8)C9—C8—H8119.9
F2—C1—C2115.5 (8)N1—C8—H8119.9
F1'—C1—C2114.3 (6)C8—C9—C10118.6 (5)
F3'—C1—C2115.0 (6)C8—C9—H9120.7
F2'—C1—C2113.1 (6)C10—C9—H9120.7
F3—C1—C2116.2 (7)C9—C10—C11120.6 (6)
C3—C2—C7118.3 (5)C9—C10—H10119.7
C3—C2—C1118.5 (5)C11—C10—H10119.7
C7—C2—C1123.1 (5)C12—C11—C10119.0 (5)
C2—C3—C4120.3 (5)C12—C11—H11120.5
C2—C3—H3119.9C10—C11—H11120.5
C4—C3—H3119.9N1—C12—C11119.6 (5)
C5—C4—C3121.2 (5)N1—C12—H12120.2
C5—C4—H4119.4C11—C12—H12120.2
C3—C4—H4119.4

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O30.861.992.781 (6)153
C4—H4···O1i0.932.563.255 (7)132
C8—H8···O20.932.473.192 (7)136
C8—H8···O3ii0.932.453.233 (8)142
C9—H9···O1ii0.932.433.274 (6)151
C11—H11···O2iii0.932.523.214 (8)132
C12—H12···O1iv0.932.423.324 (7)166

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2593).

References

  • Bats, J. W., Heinrich, T. & Reggelin, M. (1999). Acta Cryst. C55, IUC9900121.
  • Bernhard, P., Bürgi, H. B., Hauser, J., Lehmann, H. & Ludi, A. (1982). Inorg. Chem.21, 3936–3941.
  • Bruker (2000). SMART, SADABS and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Djinović, K. & Golič, L. (1992). Acta Cryst. C48, 1046–1048.
  • Kozioł, A. E. & Podlowińska, H. (1983). Acta Cryst. C39, 1373–1374.
  • Otomo, S. (1993). Eur. Patent No. 0569884B1.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Ziemer, B. & Rabis, A. (2000). Acta Cryst. C56, e94. [PubMed]

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