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

Quan, G.; Luo, A.; Cheng, W.; Xu, J.

doi:10.1107/S1600536809037325

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2500

doi:10.1107/S1600536809037325

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

Gui-xiang Quan,^a ^* Ai-lan Luo,^b Wei-hua Cheng ^c and Jia-ying Xu ^b

^aThe Experiment Center of Chemical Engineering, College of Chemical and Biological Engineering, Yancheng Institute of Technology, Yinbing Road No. 9 Yancheng, Yancheng 224051, People's Republic of China, ^bDepartment of Applied Chemistry, College of Chemical and Biological Engineering, Yancheng Institute of Technology, Yinbing Road No. 9 Yancheng, Yancheng 224051, People's Republic of China, and ^cDepartment of Chemical Engineering, Yancheng College of Textile Technology, Liberation Road S. No.265 Yancheng, Yancheng 224005, People's Republic of China
^*Correspondence e-mail: xujiaying-1984@163.com

(Received 10 September 2009; accepted 15 September 2009; online 19 September 2009)

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 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₆H₄F₃NO₂S
M_r = 211.16
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.048
wR(F²) = 0.158
S = 1.15
1494 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯Nⁱ	0.82	2.02	2.820 (3)	166
C1—H1A⋯O1ⁱⁱ	0.96	2.34	3.277 (4)	166
Symmetry codes: (i) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x-1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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.

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

Crystal data top

C₆H₄F₃NO₂S	F(000) = 424
M_r = 211.16	D_x = 1.696 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 4.961 (1) Å	θ = 10–14°
b = 15.682 (3) Å	µ = 0.41 mm⁻¹
c = 10.632 (2) Å	T = 293 K
β = 90.35 (3)°	Block, colourless
V = 827.1 (3) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1209 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.018
Graphite monochromator	θ_max = 25.3°, θ_min = 2.3°
ω/2θ scans	h = 0→5
Absorption correction: ψ scan (North et al., 1968)	k = 0→18
T_min = 0.888, T_max = 0.960	l = −12→12
1672 measured reflections	3 standard reflections every 200 reflections
1494 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.158	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max < 0.001
1494 reflections	Δρ_max = 0.33 e Å⁻³
119 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.050 (8)

Crystal data top

C₆H₄F₃NO₂S	V = 827.1 (3) Å³
M_r = 211.16	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.961 (1) Å	µ = 0.41 mm⁻¹
b = 15.682 (3) Å	T = 293 K
c = 10.632 (2) Å	0.30 × 0.20 × 0.10 mm
β = 90.35 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1209 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.018
T_min = 0.888, T_max = 0.960	3 standard reflections every 200 reflections
1672 measured reflections	intensity decay: 1%
1494 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 1.15	Δρ_max = 0.33 e Å⁻³
1494 reflections	Δρ_min = −0.25 e Å⁻³
119 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
S	1.03912 (15)	0.13345 (4)	0.21544 (7)	0.0482 (4)
N	0.7571 (4)	0.22213 (14)	0.3665 (2)	0.0406 (6)
F1	1.1047 (4)	0.41020 (12)	0.3353 (2)	0.0813 (7)
F2	0.7272 (5)	0.38613 (12)	0.4214 (2)	0.0844 (8)
F3	0.7499 (4)	0.41298 (12)	0.2261 (2)	0.0816 (7)
O1	1.2183 (5)	0.35504 (14)	0.0770 (2)	0.0683 (7)
O2	1.4044 (4)	0.22652 (13)	0.0592 (2)	0.0647 (7)
H2A	1.4972	0.2497	0.0056	0.097*
C1	0.6926 (6)	0.06626 (19)	0.3979 (3)	0.0569 (8)
H1A	0.5699	0.0842	0.4621	0.085*
H1B	0.8346	0.0330	0.4351	0.085*
H1C	0.5978	0.0324	0.3368	0.085*
C2	0.8109 (6)	0.14311 (16)	0.3348 (3)	0.0426 (7)
C3	1.0636 (5)	0.24181 (18)	0.2054 (2)	0.0401 (7)
C4	0.8996 (5)	0.27820 (16)	0.2937 (2)	0.0381 (6)
C5	1.2368 (5)	0.28263 (18)	0.1076 (2)	0.0431 (7)
C6	0.8700 (6)	0.37191 (17)	0.3191 (3)	0.0465 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0564 (5)	0.0417 (5)	0.0467 (5)	0.0035 (3)	0.0250 (4)	−0.0018 (3)
N	0.0444 (13)	0.0400 (12)	0.0374 (12)	0.0008 (9)	0.0163 (10)	0.0033 (9)
F1	0.0727 (14)	0.0560 (12)	0.1153 (19)	−0.0172 (10)	0.0111 (12)	−0.0146 (11)
F2	0.1252 (18)	0.0513 (11)	0.0775 (15)	−0.0002 (10)	0.0667 (13)	−0.0088 (9)
F3	0.1088 (19)	0.0586 (12)	0.0774 (15)	0.0297 (11)	0.0010 (13)	0.0105 (10)
O1	0.0765 (17)	0.0537 (14)	0.0752 (17)	0.0031 (11)	0.0441 (13)	0.0126 (11)
O2	0.0737 (15)	0.0559 (13)	0.0651 (15)	0.0091 (10)	0.0492 (12)	0.0065 (10)
C1	0.068 (2)	0.0435 (16)	0.0600 (19)	−0.0010 (14)	0.0290 (16)	0.0046 (13)
C2	0.0462 (15)	0.0416 (15)	0.0403 (15)	0.0016 (11)	0.0174 (12)	0.0002 (11)
C3	0.0378 (14)	0.0461 (15)	0.0366 (14)	0.0000 (10)	0.0136 (11)	−0.0002 (11)
C4	0.0364 (13)	0.0431 (15)	0.0348 (14)	−0.0009 (10)	0.0110 (11)	0.0019 (10)
C5	0.0420 (15)	0.0515 (17)	0.0360 (14)	−0.0011 (12)	0.0153 (12)	−0.0004 (12)
C6	0.0533 (17)	0.0416 (14)	0.0447 (16)	−0.0004 (12)	0.0212 (14)	0.0030 (12)

Geometric parameters (Å, º) top

S—C3	1.707 (3)	O2—H2A	0.8200
S—C2	1.712 (3)	C1—C2	1.501 (4)
N—C2	1.312 (3)	C1—H1A	0.9600
N—C4	1.371 (3)	C1—H1B	0.9600
F1—C6	1.320 (3)	C1—H1C	0.9600
F2—C6	1.321 (3)	C3—C4	1.371 (3)
F3—C6	1.319 (3)	C3—C5	1.496 (4)
O1—C5	1.185 (3)	C4—C6	1.501 (4)
O2—C5	1.317 (3)

C3—S—C2	90.35 (12)	C5—C3—S	120.7 (2)
C2—N—C4	110.8 (2)	N—C4—C3	115.5 (3)
C5—O2—H2A	109.5	N—C4—C6	118.4 (2)
C2—C1—H1A	109.5	C3—C4—C6	126.1 (2)
C2—C1—H1B	109.5	O1—C5—O2	125.5 (2)
H1A—C1—H1B	109.5	O1—C5—C3	123.9 (2)
C2—C1—H1C	109.5	O2—C5—C3	110.6 (2)
H1A—C1—H1C	109.5	F3—C6—F1	105.6 (2)
H1B—C1—H1C	109.5	F3—C6—F2	107.0 (3)
N—C2—C1	124.3 (2)	F1—C6—F2	107.0 (3)
N—C2—S	114.24 (19)	F3—C6—C4	112.8 (2)
C1—C2—S	121.5 (2)	F1—C6—C4	112.4 (2)
C4—C3—C5	130.1 (3)	F2—C6—C4	111.5 (2)
C4—C3—S	109.18 (19)

C4—N—C2—C1	178.7 (3)	S—C3—C4—C6	177.7 (2)
C4—N—C2—S	0.3 (3)	C4—C3—C5—O1	−14.8 (5)
C3—S—C2—N	−0.5 (2)	S—C3—C5—O1	162.6 (3)
C3—S—C2—C1	−179.0 (3)	C4—C3—C5—O2	166.9 (3)
C2—S—C3—C4	0.6 (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—C3	0.1 (3)	C3—C4—C6—F3	68.6 (4)
C2—N—C4—C6	−178.2 (2)	N—C4—C6—F1	127.4 (3)
C5—C3—C4—N	177.1 (3)	C3—C4—C6—F1	−50.7 (4)
S—C3—C4—N	−0.5 (3)	N—C4—C6—F2	7.2 (4)
C5—C3—C4—C6	−4.7 (4)	C3—C4—C6—F2	−170.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···Nⁱ	0.82	2.02	2.820 (3)	166
C1—H1A···O1ⁱⁱ	0.96	2.34	3.277 (4)	166

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

Experimental details

Crystal data
Chemical formula	C₆H₄F₃NO₂S
M_r	211.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	4.961 (1), 15.682 (3), 10.632 (2)
β (°)	90.35 (3)
V (Å³)	827.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.888, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	1672, 1494, 1209
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.158, 1.15
No. of reflections	1494
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.25

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···Nⁱ	0.82	2.02	2.820 (3)	166
C1—H1A···O1ⁱⁱ	0.96	2.34	3.277 (4)	166

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

Acknowledgements

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.

References

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