Ethyl 2-phenyl-5-trifluoro­methyl-1,3-thia­zole-4-carboxyl­ate

Jiang, H.-Z.; Wan, W.; Shao, M.; Hao, J.

doi:10.1107/S1600536808030389

organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o2004

doi:10.1107/S1600536808030389

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Ethyl 2-phenyl-5-trifluoromethyl-1,3-thiazole-4-carboxylate

Hai-Zhen Jiang,^a Wen Wan,^a Min Shao ^b and Jian Hao ^a,^c ^*

^aDepartment of Chemistry, College of Sciences, Shanghai University, Shanghai 200444, People's Republic of China, ^bInstrument Analysis & Research Center, Shanghai University, Shanghai 200444, People's Republic of China, and ^cKey Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People's Republic of China
^*Correspondence e-mail: jhao@staff.shu.edu.cn

(Received 17 September 2008; accepted 22 September 2008; online 24 September 2008)

In the title compound, C₁₃H₁₀F₃NO₂S, the dihedral angle between the thiazole and phenyl rings is 5.15 (1)°. No intermolecular hydrogen bonding is observed in the crystal structure.

Related literature

For general backgroud, see: Sasse et al. (2002 ); Campeau et al. (2008 ); Zificsak & Hlasta (2004 ); Rynbrandt et al. (1981 ). For a related structure, see: Kennedy et al. (2004 ).

Experimental

Crystal data

C₁₃H₁₀F₃NO₂S
M_r = 301.28
Monoclinic, P 2₁ /c
a = 8.930 (3) Å
b = 21.232 (6) Å
c = 7.574 (2) Å
β = 110.861 (4)°
V = 1342.0 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 296 (2) K
0.30 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.922, T_max = 0.973
6891 measured reflections
2367 independent reflections
1417 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.142
S = 1.01
2367 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.19 e Å⁻³

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808030389/xu2454sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030389/xu2454Isup2.hkl

checkCIF report

Comment top

1,3-Thiazole derivatives have attracted considerable attention because of various biological activities (Sasse et al., 2002) and have broad applications in the materials science (Campeau et al., 2008). Thiazole can be used as a core for developing pharmaceutically important molecules (Zificsak & Hlasta, 2004). Trifluoromethyl substituted thiazole may be the most promising skeleton in medicinal chemistry (Rynbrandt et al., 1981). The title compound, multiple substitute 1,3-thiazol with trifluoromethyl group at 5-position, has been obtained unexpectedly in the laboratory during trying to prepare 3-chloro-2-dibenzylamino-4,4,4-trifluoro-butyric acid ethyl ester by a reaction of 2-dibenzylamino-4,4,4-trifluoro-3-hydroxy-butyric acid ethyl ester with thionyl chloride. We present here the crystal structure of the title compound.

The molecular structure is shown in Fig. 1. The bond lengths in the thiazole moiety agree with those found in methyl 2-amino-5-isopropyl-1,3-thiazole-4-carboxylate (Kennedy et al., 2004). The thiazole ring makes a dihedral angle of 5.15 (1)° with phenyl ring, showing the approximately coplanar molecular structure except for trifluoromethyl and ethoxy group. No intermolecular hydrogen bonding is observed in the crystal structure.

Related literature top

For general backgroud, see: Sasse et al. (2002); Campeau et al. (2008); Zificsak & Hlasta (2004); Rynbrandt et al. (1981). For a related structure, see: Kennedy et al. (2004).

Experimental top

A solution of 2-dibenzylamino-4, 4, 4-trifluoro-3-hydroxy-butyric acid ethyl ester (0.2 mmol) in 10 ml thionyl chloride was refluxed for a period of half an hour till the complete consumption of raw material. Excess thionyl chloride was evaporated, the residue was diluted with anhydrous ethanol (4 ml), then concentrated by rotary evaporator. The crude product was re-crystallized from ethanol (95%) and colorless needle-type crystals of (I) were obtained.

Computing details top

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

Figures top

Fig. 1. View of the title compound (I), shown the atom labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented by circles of arbitrary radii.

Ethyl 2-phenyl-5-trifluoromethyl-1,3-thiazole-4-carboxylate top

Crystal data top

C₁₃H₁₀F₃NO₂S	F(000) = 616
M_r = 301.28	D_x = 1.491 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 320 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.930 (3) Å	Cell parameters from 1005 reflections
b = 21.232 (6) Å	θ = 2.5–19.0°
c = 7.574 (2) Å	µ = 0.28 mm⁻¹
β = 110.861 (4)°	T = 296 K
V = 1342.0 (7) Å³	Needle, colorless
Z = 4	0.30 × 0.10 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2367 independent reflections
Radiation source: fine-focus sealed tube	1417 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.922, T_max = 0.973	k = −25→19
6891 measured reflections	l = −8→8

Refinement top

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0642P)²] where P = (F_o² + 2F_c²)/3
2367 reflections	(Δ/σ)_max = 0.001
182 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₃H₁₀F₃NO₂S	V = 1342.0 (7) Å³
M_r = 301.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.930 (3) Å	µ = 0.28 mm⁻¹
b = 21.232 (6) Å	T = 296 K
c = 7.574 (2) Å	0.30 × 0.10 × 0.10 mm
β = 110.861 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2367 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1417 reflections with I > 2σ(I)
T_min = 0.922, T_max = 0.973	R_int = 0.050
6891 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.142	H-atom parameters constrained
S = 1.01	Δρ_max = 0.22 e Å⁻³
2367 reflections	Δρ_min = −0.19 e Å⁻³
182 parameters

Special details top

Experimental. IR (KBr, cm^-1): 3061, 2980, 1737, 1633, 1513, 1461, 1290, 1210, 766, 689. ¹H NMR (CDCl₃, 500 MHz). δ/p.p.m.: 7.46–8.00 (m, 5H), 4.49 (q, J = 7.0 Hz, 2H), 1.44 (t, J = 7.0 Hz, 3H). ¹³C NMR (CDCl₃, 125 MHz). δ/p.p.m.: 168.87, 160.27, 146.48, 131.77, 131.63, 129.24, 164.15 (q, ²J_C—F = 36.5 Hz, CF₃C–), 123.33 (q, ¹J_C—F = 269.3 Hz, –CF₃), 62.41, 13.98. ¹⁹F NMR (CDCl₃, 470 MHz, CFCl₃). δ/p.p.m.: -52.44 (s).

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) top

	x	y	z	U_iso*/U_eq
S1	0.22302 (11)	0.67958 (4)	0.44789 (13)	0.0585 (3)
C1	0.1690 (4)	0.75511 (15)	0.3693 (5)	0.0504 (8)
C2	0.2697 (4)	0.80979 (15)	0.4545 (5)	0.0523 (8)
C3	0.4186 (4)	0.80233 (17)	0.5954 (5)	0.0615 (10)
H3	0.4559	0.7622	0.6376	0.074*
C4	0.5115 (4)	0.85408 (19)	0.6732 (5)	0.0681 (10)
H4	0.6116	0.8488	0.7671	0.082*
C5	0.4564 (5)	0.91329 (18)	0.6123 (6)	0.0720 (11)
H5	0.5192	0.9483	0.6646	0.086*
C6	0.3083 (5)	0.92108 (18)	0.4743 (6)	0.0741 (11)
H6	0.2708	0.9614	0.4343	0.089*
C7	0.2154 (4)	0.86972 (16)	0.3947 (5)	0.0642 (10)
H7	0.1156	0.8753	0.3004	0.077*
C8	−0.0328 (4)	0.70143 (16)	0.1739 (5)	0.0514 (8)
C9	0.0515 (4)	0.65213 (16)	0.2791 (5)	0.0517 (8)
C10	0.0138 (5)	0.58379 (17)	0.2771 (6)	0.0674 (10)
C11	−0.1837 (4)	0.69976 (18)	0.0062 (5)	0.0577 (9)
C12	−0.3482 (5)	0.63721 (19)	−0.2455 (6)	0.0857 (13)
H12A	−0.3442	0.6683	−0.3375	0.103*
H12B	−0.4455	0.6438	−0.2188	0.103*
C13	−0.3463 (7)	0.5732 (2)	−0.3197 (7)	0.133 (2)
H13A	−0.2565	0.5689	−0.3603	0.200*
H13B	−0.4438	0.5660	−0.4249	0.200*
H13C	−0.3375	0.5429	−0.2224	0.200*
F1	−0.1303 (3)	0.57367 (10)	0.2825 (4)	0.0973 (8)
F2	0.0198 (3)	0.55287 (10)	0.1294 (4)	0.0932 (8)
F3	0.1174 (3)	0.55518 (10)	0.4280 (4)	0.1071 (9)
N1	0.0337 (3)	0.75955 (12)	0.2277 (4)	0.0522 (7)
O1	−0.2677 (3)	0.74436 (12)	−0.0528 (4)	0.0791 (8)
O2	−0.2081 (3)	0.64335 (11)	−0.0726 (3)	0.0693 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0601 (6)	0.0546 (6)	0.0597 (6)	0.0055 (4)	0.0201 (5)	0.0032 (4)
C1	0.053 (2)	0.054 (2)	0.053 (2)	0.0023 (16)	0.0291 (19)	0.0011 (16)
C2	0.058 (2)	0.055 (2)	0.049 (2)	0.0007 (17)	0.0249 (18)	−0.0021 (17)
C3	0.060 (2)	0.057 (2)	0.069 (3)	0.0017 (18)	0.024 (2)	0.0034 (18)
C4	0.058 (2)	0.075 (3)	0.066 (3)	−0.007 (2)	0.016 (2)	−0.003 (2)
C5	0.074 (3)	0.058 (3)	0.086 (3)	−0.010 (2)	0.030 (2)	−0.010 (2)
C6	0.073 (3)	0.057 (2)	0.089 (3)	0.004 (2)	0.024 (2)	−0.005 (2)
C7	0.063 (2)	0.054 (2)	0.070 (3)	0.0019 (18)	0.015 (2)	−0.0032 (18)
C8	0.053 (2)	0.049 (2)	0.057 (2)	0.0039 (16)	0.0256 (19)	−0.0011 (17)
C9	0.0499 (19)	0.054 (2)	0.057 (2)	0.0036 (16)	0.0259 (17)	−0.0019 (17)
C10	0.070 (3)	0.054 (2)	0.076 (3)	0.0024 (19)	0.022 (2)	0.003 (2)
C11	0.056 (2)	0.056 (2)	0.063 (2)	0.0018 (18)	0.023 (2)	0.0041 (19)
C12	0.084 (3)	0.079 (3)	0.073 (3)	−0.004 (2)	0.003 (2)	−0.001 (2)
C13	0.172 (5)	0.076 (4)	0.103 (4)	0.002 (3)	−0.012 (4)	−0.012 (3)
F1	0.0903 (17)	0.0681 (15)	0.149 (2)	−0.0148 (12)	0.0613 (17)	0.0074 (14)
F2	0.118 (2)	0.0605 (14)	0.109 (2)	0.0018 (12)	0.0492 (16)	−0.0211 (13)
F3	0.123 (2)	0.0591 (15)	0.108 (2)	0.0033 (13)	0.0028 (17)	0.0185 (13)
N1	0.0500 (18)	0.0519 (18)	0.0575 (18)	0.0012 (13)	0.0227 (16)	0.0024 (13)
O1	0.0707 (18)	0.0663 (18)	0.083 (2)	0.0126 (14)	0.0060 (15)	0.0000 (14)
O2	0.0701 (16)	0.0554 (16)	0.0701 (18)	−0.0010 (12)	0.0100 (14)	−0.0024 (13)

Geometric parameters (Å, º) top

S1—C9	1.710 (3)	C8—C9	1.367 (4)
S1—C1	1.719 (3)	C8—C11	1.487 (5)
C1—N1	1.302 (4)	C9—C10	1.489 (5)
C1—C2	1.470 (5)	C10—F2	1.315 (4)
C2—C7	1.380 (4)	C10—F1	1.319 (4)
C2—C3	1.386 (5)	C10—F3	1.334 (4)
C3—C4	1.376 (5)	C11—O1	1.192 (4)
C3—H3	0.9300	C11—O2	1.321 (4)
C4—C5	1.369 (5)	C12—O2	1.459 (4)
C4—H4	0.9300	C12—C13	1.474 (5)
C5—C6	1.373 (5)	C12—H12A	0.9700
C5—H5	0.9300	C12—H12B	0.9700
C6—C7	1.373 (5)	C13—H13A	0.9600
C6—H6	0.9300	C13—H13B	0.9600
C7—H7	0.9300	C13—H13C	0.9600
C8—N1	1.367 (4)

C9—S1—C1	89.59 (17)	C8—C9—S1	109.6 (3)
N1—C1—C2	123.2 (3)	C10—C9—S1	118.6 (3)
N1—C1—S1	114.6 (2)	F2—C10—F1	106.3 (3)
C2—C1—S1	122.2 (3)	F2—C10—F3	106.0 (3)
C7—C2—C3	119.1 (3)	F1—C10—F3	106.6 (3)
C7—C2—C1	119.7 (3)	F2—C10—C9	114.7 (3)
C3—C2—C1	121.1 (3)	F1—C10—C9	112.2 (3)
C4—C3—C2	120.3 (3)	F3—C10—C9	110.5 (3)
C4—C3—H3	119.8	O1—C11—O2	124.8 (4)
C2—C3—H3	119.8	O1—C11—C8	124.0 (3)
C5—C4—C3	120.0 (4)	O2—C11—C8	111.2 (3)
C5—C4—H4	120.0	O2—C12—C13	107.6 (4)
C3—C4—H4	120.0	O2—C12—H12A	110.2
C4—C5—C6	120.0 (4)	C13—C12—H12A	110.2
C4—C5—H5	120.0	O2—C12—H12B	110.2
C6—C5—H5	120.0	C13—C12—H12B	110.2
C5—C6—C7	120.4 (4)	H12A—C12—H12B	108.5
C5—C6—H6	119.8	C12—C13—H13A	109.5
C7—C6—H6	119.8	C12—C13—H13B	109.5
C6—C7—C2	120.1 (4)	H13A—C13—H13B	109.5
C6—C7—H7	119.9	C12—C13—H13C	109.5
C2—C7—H7	119.9	H13A—C13—H13C	109.5
N1—C8—C9	115.3 (3)	H13B—C13—H13C	109.5
N1—C8—C11	116.2 (3)	C1—N1—C8	110.9 (3)
C9—C8—C11	128.5 (3)	C11—O2—C12	115.9 (3)
C8—C9—C10	131.6 (3)

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀F₃NO₂S
M_r	301.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.930 (3), 21.232 (6), 7.574 (2)
β (°)	110.861 (4)
V (Å³)	1342.0 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.922, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	6891, 2367, 1417
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.142, 1.01
No. of reflections	2367
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.19

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors are grateful for financial support from the Natural Science Foundation of China (No. 20772079) and the Science Foundation of Shanghai Municipal Commission of Sciences and Technology (07JC14020, 07ZR14040), and for structural analysis by the Instrumental Analysis & Research Center of Shanghai University.

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