2-Benzyl­sulfanyl-3-(2,2,2-trifluoro­ethoxy)pyridine

Feng, Z.-Q.; Yang, X.-L.; Ye, Y.-F.; Dong, T.

doi:10.1107/S1600536810043308

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3093

https://doi.org/10.1107/S1600536810043308

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2-Benzylsulfanyl-3-(2,2,2-trifluoroethoxy)pyridine

Zhi-Qiang Feng,^a ^* Xiao-Li Yang,^a Yuan-Feng Ye ^a and Tao Dong ^a

^aCollege of Materials Engineering, Jinling Institute of Technology, No. 99 Hongjing Street, Nanjing, Nanjing 211169, People's Republic of China
^*Correspondence e-mail: fzq@jit.edu.cn

(Received 23 October 2010; accepted 24 October 2010; online 6 November 2010)

The title compound, C₁₄H₁₂F₃NOS, was synthesized by the reaction of 2-chloro-3-(2,2,2-trifluoroethoxy)pyridine and phenylmethanethiol. The dihedral angle between the aromatic rings is 76.7 (2)°. In the crystal structure, weak aromatic π–π stacking between inversion-related pairs of pyridine rings [centroid-to-centroid separation = 3.776 (2) Å] may help to establish the packing.

Related literature

For background to the title compound as a precursor of weedkillers, see: Howard et al. (2001 ). For reference bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₁₂F₃NOS
M_r = 299.31
Monoclinic, P 2₁ /n
a = 8.3770 (17) Å
b = 16.860 (3) Å
c = 10.144 (2) Å
β = 97.32 (3)°
V = 1421.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.927, T_max = 0.951
2758 measured reflections
2575 independent reflections
1716 reflections with I > 2σ(I)
R_int = 0.036
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.136
S = 1.01
2575 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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: https://doi.org/10.1107/S1600536810043308/hb5702sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810043308/hb5702Isup2.hkl

checkCIF report

Comment top

3-(2,2,2-trifluoroethoxy)-2-(benzylthio)pyridine, (I), is an important intermediate for a novel weed killer N-[[(4,6-Dimethoxy-2-Pyrimidinyl)Amino]Carbonyl]- 3-(2,2,2-Trifluoroethoxy)-2-Pyridinesulfonamide, which is of high herbicidal activity and friendly to the environment (Howard et al., 2001).

Here we report the crystal structure of (I). In the molecule of the title compound (Fig. 1), all bond lengths and angles (Allen et al., 1987) are within normal ranges. Rings A (C3–C6/N/C7) and B (C9–C14) are of course planar, while the dihedral angle between them is 76.7 (2)°.

Related literature top

For background to the title compound as a precursor of weedkillers, see: Howard et al. (2001). For reference bond-length data, see: Allen et al. (1987).

Experimental top

3-(2,2,2-trifluoroethoxy)-2-chloropyridine (10 mmol) and potassium carbonate (20 mmol) were dissolved in DMF (20 ml), and the mixture was stirred at reflux for 1 h. Then phenylmethanethiol (12 mmol) was added dropwise to the mixture above, refluxed for another 6 h. After cooling and filtering, crude compound (I) was obtained. Pure product suitable for X-ray diffraction was recrystallized from alcohol as colourless blocks of (I).

Structure description top

For background to the title compound as a precursor of weedkillers, see: Howard et al. (2001). For reference bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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. The molecular structure of the title molecule, with displacement ellipsoids drawn at the 50% probability level.

2-Benzylsulfanyl-3-(2,2,2-trifluoroethoxy)pyridine top

Crystal data top

C₁₄H₁₂F₃NOS	F(000) = 616
M_r = 299.31	D_x = 1.399 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 353 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 8.3770 (17) Å	Cell parameters from 25 reflections
b = 16.860 (3) Å	θ = 9–13°
c = 10.144 (2) Å	µ = 0.26 mm⁻¹
β = 97.32 (3)°	T = 293 K
V = 1421.0 (5) Å³	Block, colourless
Z = 4	0.30 × 0.20 × 0.20 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1716 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.036
Graphite monochromator	θ_max = 25.3°, θ_min = 2.4°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→20
T_min = 0.927, T_max = 0.951	l = −12→12
2758 measured reflections	3 standard reflections every 200 reflections
2575 independent reflections	intensity decay: none

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)] = 0.058	H-atom parameters constrained
wR(F²) = 0.136	w = 1/[σ²(F_o²) + (0.027P)² + 2.174P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2575 reflections	Δρ_max = 0.26 e Å⁻³
182 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.049 (2)

Crystal data top

C₁₄H₁₂F₃NOS	V = 1421.0 (5) Å³
M_r = 299.31	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.3770 (17) Å	µ = 0.26 mm⁻¹
b = 16.860 (3) Å	T = 293 K
c = 10.144 (2) Å	0.30 × 0.20 × 0.20 mm
β = 97.32 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1716 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.036
T_min = 0.927, T_max = 0.951	3 standard reflections every 200 reflections
2758 measured reflections	intensity decay: none
2575 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.01	Δρ_max = 0.26 e Å⁻³
2575 reflections	Δρ_min = −0.28 e Å⁻³
182 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
S1	0.18955 (13)	0.37494 (6)	0.26098 (10)	0.0562 (3)
O1	−0.0642 (3)	0.33867 (16)	0.0614 (3)	0.0602 (8)
N1	0.2971 (4)	0.45168 (18)	0.0576 (3)	0.0516 (8)
F1	−0.2695 (4)	0.21214 (19)	0.1032 (4)	0.1275 (14)
F2	−0.4629 (4)	0.2729 (2)	−0.0088 (4)	0.1367 (14)
F3	−0.3439 (4)	0.3240 (2)	0.1674 (3)	0.1163 (11)
C1	−0.3180 (6)	0.2823 (3)	0.0625 (6)	0.0831 (15)
C2	−0.2097 (5)	0.3222 (3)	−0.0197 (4)	0.0667 (12)
H2A	−0.1897	0.2882	−0.0930	0.080*
H2B	−0.2582	0.3710	−0.0560	0.080*
C3	0.0459 (4)	0.3844 (2)	0.0070 (4)	0.0463 (9)
C4	0.0345 (5)	0.4081 (3)	−0.1235 (4)	0.0607 (11)
H4A	−0.0530	0.3936	−0.1846	0.073*
C5	0.1580 (5)	0.4542 (3)	−0.1607 (4)	0.0678 (12)
H5A	0.1544	0.4714	−0.2482	0.081*
C6	0.2844 (5)	0.4742 (2)	−0.0694 (4)	0.0592 (11)
H6A	0.3661	0.5051	−0.0966	0.071*
C7	0.1804 (4)	0.4077 (2)	0.0952 (3)	0.0427 (8)
C8	0.3643 (5)	0.4284 (2)	0.3398 (4)	0.0550 (10)
H8A	0.4075	0.4004	0.4201	0.066*
H8B	0.4463	0.4285	0.2804	0.066*
C9	0.3294 (4)	0.5127 (2)	0.3752 (3)	0.0432 (9)
C10	0.4057 (4)	0.5758 (2)	0.3243 (4)	0.0499 (9)
H10A	0.4780	0.5663	0.2637	0.060*
C11	0.3776 (5)	0.6527 (2)	0.3611 (4)	0.0591 (11)
H11A	0.4310	0.6943	0.3254	0.071*
C12	0.2721 (5)	0.6681 (3)	0.4494 (5)	0.0704 (13)
H12A	0.2528	0.7200	0.4739	0.084*
C13	0.1939 (5)	0.6058 (3)	0.5023 (5)	0.0730 (13)
H13A	0.1226	0.6157	0.5635	0.088*
C14	0.2214 (5)	0.5291 (3)	0.4647 (4)	0.0593 (11)
H14A	0.1668	0.4877	0.4997	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0704 (7)	0.0507 (6)	0.0449 (5)	−0.0104 (5)	−0.0025 (5)	0.0047 (5)
O1	0.0537 (16)	0.0634 (17)	0.0608 (17)	−0.0163 (14)	−0.0029 (13)	0.0096 (14)
N1	0.0501 (19)	0.054 (2)	0.0519 (19)	−0.0038 (16)	0.0119 (15)	−0.0019 (16)
F1	0.113 (3)	0.073 (2)	0.206 (4)	−0.0068 (19)	0.059 (3)	0.037 (2)
F2	0.063 (2)	0.165 (4)	0.182 (4)	−0.039 (2)	0.013 (2)	−0.008 (3)
F3	0.119 (3)	0.121 (3)	0.120 (3)	−0.018 (2)	0.055 (2)	−0.021 (2)
C1	0.063 (3)	0.076 (4)	0.114 (4)	−0.014 (3)	0.024 (3)	−0.016 (3)
C2	0.054 (3)	0.065 (3)	0.080 (3)	−0.016 (2)	0.005 (2)	−0.012 (2)
C3	0.045 (2)	0.046 (2)	0.047 (2)	−0.0015 (17)	0.0027 (17)	−0.0018 (17)
C4	0.059 (3)	0.076 (3)	0.044 (2)	−0.002 (2)	−0.0020 (19)	−0.001 (2)
C5	0.077 (3)	0.084 (3)	0.043 (2)	−0.002 (3)	0.012 (2)	0.010 (2)
C6	0.060 (3)	0.065 (3)	0.056 (3)	−0.004 (2)	0.022 (2)	0.002 (2)
C7	0.044 (2)	0.0412 (19)	0.0415 (19)	0.0020 (16)	0.0023 (16)	−0.0037 (16)
C8	0.059 (2)	0.057 (2)	0.045 (2)	0.004 (2)	−0.0091 (18)	−0.0034 (18)
C9	0.0396 (19)	0.051 (2)	0.0363 (19)	0.0028 (17)	−0.0076 (15)	−0.0015 (16)
C10	0.044 (2)	0.058 (2)	0.045 (2)	0.0031 (19)	−0.0003 (17)	0.0016 (18)
C11	0.054 (2)	0.055 (2)	0.065 (3)	0.000 (2)	−0.006 (2)	0.008 (2)
C12	0.067 (3)	0.057 (3)	0.083 (3)	0.011 (2)	−0.005 (3)	−0.015 (2)
C13	0.067 (3)	0.083 (3)	0.072 (3)	0.007 (3)	0.019 (2)	−0.017 (3)
C14	0.059 (3)	0.064 (3)	0.056 (2)	−0.004 (2)	0.011 (2)	0.001 (2)

Geometric parameters (Å, º) top

S1—C7	1.762 (4)	C5—H5A	0.9300
S1—C8	1.816 (4)	C6—H6A	0.9300
O1—C3	1.371 (4)	C8—C9	1.504 (5)
O1—C2	1.409 (4)	C8—H8A	0.9700
N1—C7	1.321 (4)	C8—H8B	0.9700
N1—C6	1.334 (5)	C9—C10	1.375 (5)
F1—C1	1.300 (6)	C9—C14	1.389 (5)
F2—C1	1.341 (6)	C10—C11	1.378 (5)
F3—C1	1.316 (6)	C10—H10A	0.9300
C1—C2	1.472 (6)	C11—C12	1.361 (6)
C2—H2A	0.9700	C11—H11A	0.9300
C2—H2B	0.9700	C12—C13	1.382 (6)
C3—C4	1.374 (5)	C12—H12A	0.9300
C3—C7	1.403 (5)	C13—C14	1.375 (6)
C4—C5	1.385 (6)	C13—H13A	0.9300
C4—H4A	0.9300	C14—H14A	0.9300
C5—C6	1.358 (5)

C7—S1—C8	101.50 (18)	N1—C7—C3	122.4 (3)
C3—O1—C2	116.9 (3)	N1—C7—S1	120.5 (3)
C7—N1—C6	117.9 (3)	C3—C7—S1	117.0 (3)
F1—C1—F3	107.8 (5)	C9—C8—S1	113.8 (3)
F1—C1—F2	106.8 (4)	C9—C8—H8A	108.8
F3—C1—F2	105.6 (4)	S1—C8—H8A	108.8
F1—C1—C2	113.9 (4)	C9—C8—H8B	108.8
F3—C1—C2	113.0 (4)	S1—C8—H8B	108.8
F2—C1—C2	109.2 (5)	H8A—C8—H8B	107.7
O1—C2—C1	108.0 (4)	C10—C9—C14	117.7 (4)
O1—C2—H2A	110.1	C10—C9—C8	121.8 (3)
C1—C2—H2A	110.1	C14—C9—C8	120.5 (4)
O1—C2—H2B	110.1	C9—C10—C11	121.5 (4)
C1—C2—H2B	110.1	C9—C10—H10A	119.2
H2A—C2—H2B	108.4	C11—C10—H10A	119.2
O1—C3—C4	125.7 (3)	C12—C11—C10	120.3 (4)
O1—C3—C7	115.3 (3)	C12—C11—H11A	119.8
C4—C3—C7	119.0 (3)	C10—C11—H11A	119.8
C3—C4—C5	117.6 (4)	C11—C12—C13	119.4 (4)
C3—C4—H4A	121.2	C11—C12—H12A	120.3
C5—C4—H4A	121.2	C13—C12—H12A	120.3
C6—C5—C4	119.9 (4)	C14—C13—C12	120.2 (4)
C6—C5—H5A	120.1	C14—C13—H13A	119.9
C4—C5—H5A	120.1	C12—C13—H13A	119.9
N1—C6—C5	123.2 (4)	C13—C14—C9	121.0 (4)
N1—C6—H6A	118.4	C13—C14—H14A	119.5
C5—C6—H6A	118.4	C9—C14—H14A	119.5

C3—O1—C2—C1	−172.3 (4)	O1—C3—C7—S1	0.3 (4)
F1—C1—C2—O1	−66.8 (6)	C4—C3—C7—S1	−179.5 (3)
F3—C1—C2—O1	56.8 (6)	C8—S1—C7—N1	7.5 (3)
F2—C1—C2—O1	174.0 (4)	C8—S1—C7—C3	−173.0 (3)
C2—O1—C3—C4	−7.7 (6)	C7—S1—C8—C9	81.3 (3)
C2—O1—C3—C7	172.6 (3)	S1—C8—C9—C10	−120.4 (3)
O1—C3—C4—C5	−179.8 (4)	S1—C8—C9—C14	61.7 (4)
C7—C3—C4—C5	−0.1 (6)	C14—C9—C10—C11	0.5 (5)
C3—C4—C5—C6	0.1 (6)	C8—C9—C10—C11	−177.5 (3)
C7—N1—C6—C5	0.1 (6)	C9—C10—C11—C12	−0.1 (6)
C4—C5—C6—N1	−0.1 (7)	C10—C11—C12—C13	0.3 (6)
C6—N1—C7—C3	−0.1 (5)	C11—C12—C13—C14	−0.8 (7)
C6—N1—C7—S1	179.5 (3)	C12—C13—C14—C9	1.1 (7)
O1—C3—C7—N1	179.8 (3)	C10—C9—C14—C13	−0.9 (6)
C4—C3—C7—N1	0.1 (6)	C8—C9—C14—C13	177.1 (4)

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂F₃NOS
M_r	299.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.3770 (17), 16.860 (3), 10.144 (2)
β (°)	97.32 (3)
V (Å³)	1421.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.927, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	2758, 2575, 1716
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.136, 1.01
No. of reflections	2575
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.28

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors gratefully acknowledge Professor Hua-Qin Wang of the Analysis Center, Nanjing University, for providing the Enraf–Nonius CAD-4 diffractometer for this research project.

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. CSD CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Howard, S., Hudetz, M. & Allard, J. L. (2001). The BCPC Conference – Weeds 2001, 2A-3, pp. 29–34. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar