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

Abstract

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,

• a = 8.930 (3) Å

• b = 21.232 (6) Å

• c = 7.574 (2) Å

• β = 110.861 (4)°

• V = 1342.0 (7) ų

• 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[F ² > 2σ(F ²)] = 0.056

• wR(F ²) = 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.

Supplementary Material

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All the H atoms were placed in geometrically idealized positions and constrained to ride their parent atoms, with C—H = 0.93 - 0.97 Å and U_iso(H) = 1.5U_eq(C) for methyl and 1.2U_eq(C) for others.

Figures

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.

Crystal data

C13H10F3NO2S	F(000) = 616
Mr = 301.28	Dx = 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

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

Refinement

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(Fo2) + (0.0642P)2] where P = (Fo2 + 2Fc2)/3
2367 reflections	(Δ/σ)max = 0.001
182 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

Special details

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, 2JC—F = 36.5 Hz, CF3C–), 123.33 (q, 1JC—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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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)