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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2500.
Published online 2009 September 19. doi:  10.1107/S1600536809037325
PMCID: PMC2970299

2-Methyl-4-trifluoro­meth­yl-1,3-thia­zole-5-carboxylic acid

Abstract

In crystal of the title compound, C6H4F3NO2S, mol­ecules are linked by O—H(...)N and C—H(...)O hydrogen bonds, forming chains.

Related literature

For a related compound, see: Liu (2004 [triangle]). For reference structural data, see: Allen et al. (1987 [triangle]).

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Object name is e-65-o2500-scheme1.jpg

Experimental

Crystal data

  • C6H4F3NO2S
  • M r = 211.16
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2500-efi1.jpg
  • a = 4.961 (1) Å
  • b = 15.682 (3) Å
  • c = 10.632 (2) Å
  • β = 90.35 (3)°
  • V = 827.1 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.41 mm−1
  • T = 293 K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.888, T max = 0.960
  • 1672 measured reflections
  • 1494 independent reflections
  • 1209 reflections with I > 2σ(I)
  • R int = 0.018
  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.158
  • S = 1.15
  • 1494 reflections
  • 119 parameters
  • H-atom parameters constrained
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); 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: PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809037325/hb5094sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809037325/hb5094Isup2.hkl

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

Acknowledgments

This work was supported by the Science Fundamental Research Fund of the Education Department, Jiangsu Province (No. 06KJB150024). The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection.

supplementary crystallographic information

Experimental

To a cooled solution of methyl 2-methyl-4-(trifluoromethyl)thiazole-5-carboxylate (0.12 mol) in ethyl alcohol (200 ml) was added a solution of sodium hydroxide (9.62 g) in 200ml of water. The solution was heated at 358 K for 1.5 h. After evaporation of the ethyl alcohol, the aqueous solution was diluted with 200 ml of water and acidified to pH = 1 with concentrated aqueous hydrochloric acid. The solid material was filtered and washed twice with 100 ml of water and 100 ml of dichloromethane. After drying in a vacuum oven,the title compound was obtained (yield; 85%). Colourless blocks of (I) were obtained by slow evaporation of an ethyl acetate solution.

Refinement

The H atoms were positioned geometrically (C—H = 0.93–0.96 Å, O—H = 0.82Å) and refined as with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C, O).

Figures

Fig. 1.
The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level.
Fig. 2.
A packing diagram for (I). C—H···O hydrogen bonds are shown by dashed lines.

Crystal data

C6H4F3NO2SF(000) = 424
Mr = 211.16Dx = 1.696 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 4.961 (1) Åθ = 10–14°
b = 15.682 (3) ŵ = 0.41 mm1
c = 10.632 (2) ÅT = 293 K
β = 90.35 (3)°Block, colourless
V = 827.1 (3) Å30.30 × 0.20 × 0.10 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer1209 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.018
graphiteθmax = 25.3°, θmin = 2.3°
ω/2θ scansh = 0→5
Absorption correction: ψ scan (North et al., 1968)k = 0→18
Tmin = 0.888, Tmax = 0.960l = −12→12
1672 measured reflections3 standard reflections every 200 reflections
1494 independent reflections intensity decay: 1%

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.158w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max < 0.001
1494 reflectionsΔρmax = 0.33 e Å3
119 parametersΔρmin = −0.25 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.050 (8)

Special details

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 > 2sigma(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*/Ueq
S1.03912 (15)0.13345 (4)0.21544 (7)0.0482 (4)
N0.7571 (4)0.22213 (14)0.3665 (2)0.0406 (6)
F11.1047 (4)0.41020 (12)0.3353 (2)0.0813 (7)
F20.7272 (5)0.38613 (12)0.4214 (2)0.0844 (8)
F30.7499 (4)0.41298 (12)0.2261 (2)0.0816 (7)
O11.2183 (5)0.35504 (14)0.0770 (2)0.0683 (7)
O21.4044 (4)0.22652 (13)0.0592 (2)0.0647 (7)
H2A1.49720.24970.00560.097*
C10.6926 (6)0.06626 (19)0.3979 (3)0.0569 (8)
H1A0.56990.08420.46210.085*
H1B0.83460.03300.43510.085*
H1C0.59780.03240.33680.085*
C20.8109 (6)0.14311 (16)0.3348 (3)0.0426 (7)
C31.0636 (5)0.24181 (18)0.2054 (2)0.0401 (7)
C40.8996 (5)0.27820 (16)0.2937 (2)0.0381 (6)
C51.2368 (5)0.28263 (18)0.1076 (2)0.0431 (7)
C60.8700 (6)0.37191 (17)0.3191 (3)0.0465 (7)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S0.0564 (5)0.0417 (5)0.0467 (5)0.0035 (3)0.0250 (4)−0.0018 (3)
N0.0444 (13)0.0400 (12)0.0374 (12)0.0008 (9)0.0163 (10)0.0033 (9)
F10.0727 (14)0.0560 (12)0.1153 (19)−0.0172 (10)0.0111 (12)−0.0146 (11)
F20.1252 (18)0.0513 (11)0.0775 (15)−0.0002 (10)0.0667 (13)−0.0088 (9)
F30.1088 (19)0.0586 (12)0.0774 (15)0.0297 (11)0.0010 (13)0.0105 (10)
O10.0765 (17)0.0537 (14)0.0752 (17)0.0031 (11)0.0441 (13)0.0126 (11)
O20.0737 (15)0.0559 (13)0.0651 (15)0.0091 (10)0.0492 (12)0.0065 (10)
C10.068 (2)0.0435 (16)0.0600 (19)−0.0010 (14)0.0290 (16)0.0046 (13)
C20.0462 (15)0.0416 (15)0.0403 (15)0.0016 (11)0.0174 (12)0.0002 (11)
C30.0378 (14)0.0461 (15)0.0366 (14)0.0000 (10)0.0136 (11)−0.0002 (11)
C40.0364 (13)0.0431 (15)0.0348 (14)−0.0009 (10)0.0110 (11)0.0019 (10)
C50.0420 (15)0.0515 (17)0.0360 (14)−0.0011 (12)0.0153 (12)−0.0004 (12)
C60.0533 (17)0.0416 (14)0.0447 (16)−0.0004 (12)0.0212 (14)0.0030 (12)

Geometric parameters (Å, °)

S—C31.707 (3)O2—H2A0.8200
S—C21.712 (3)C1—C21.501 (4)
N—C21.312 (3)C1—H1A0.9600
N—C41.371 (3)C1—H1B0.9600
F1—C61.320 (3)C1—H1C0.9600
F2—C61.321 (3)C3—C41.371 (3)
F3—C61.319 (3)C3—C51.496 (4)
O1—C51.185 (3)C4—C61.501 (4)
O2—C51.317 (3)
C3—S—C290.35 (12)C5—C3—S120.7 (2)
C2—N—C4110.8 (2)N—C4—C3115.5 (3)
C5—O2—H2A109.5N—C4—C6118.4 (2)
C2—C1—H1A109.5C3—C4—C6126.1 (2)
C2—C1—H1B109.5O1—C5—O2125.5 (2)
H1A—C1—H1B109.5O1—C5—C3123.9 (2)
C2—C1—H1C109.5O2—C5—C3110.6 (2)
H1A—C1—H1C109.5F3—C6—F1105.6 (2)
H1B—C1—H1C109.5F3—C6—F2107.0 (3)
N—C2—C1124.3 (2)F1—C6—F2107.0 (3)
N—C2—S114.24 (19)F3—C6—C4112.8 (2)
C1—C2—S121.5 (2)F1—C6—C4112.4 (2)
C4—C3—C5130.1 (3)F2—C6—C4111.5 (2)
C4—C3—S109.18 (19)
C4—N—C2—C1178.7 (3)S—C3—C4—C6177.7 (2)
C4—N—C2—S0.3 (3)C4—C3—C5—O1−14.8 (5)
C3—S—C2—N−0.5 (2)S—C3—C5—O1162.6 (3)
C3—S—C2—C1−179.0 (3)C4—C3—C5—O2166.9 (3)
C2—S—C3—C40.6 (2)S—C3—C5—O2−15.7 (3)
C2—S—C3—C5−177.3 (2)N—C4—C6—F3−113.2 (3)
C2—N—C4—C30.1 (3)C3—C4—C6—F368.6 (4)
C2—N—C4—C6−178.2 (2)N—C4—C6—F1127.4 (3)
C5—C3—C4—N177.1 (3)C3—C4—C6—F1−50.7 (4)
S—C3—C4—N−0.5 (3)N—C4—C6—F27.2 (4)
C5—C3—C4—C6−4.7 (4)C3—C4—C6—F2−170.9 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2A···Ni0.822.022.820 (3)166
C1—H1A···O1ii0.962.343.277 (4)166

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5094).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Enraf–Nonius (1994). CAD-4 EXPRESS Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Liu, C.-L. (2004). J. Fluorine Chem.125, 1287–1290.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography