2,2,2-Trifluoro­ethyl 4-methyl­benzene­sulfonate

Xia, S.; Shi, Y.-B.; He, F.-F.; Wang, H.-B.

doi:10.1107/S1600536810038894

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2779

https://doi.org/10.1107/S1600536810038894

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2,2,2-Trifluoroethyl 4-methylbenzenesulfonate

Song Xia,^a,^b Ya-Bin Shi,^a,^b Fei-Fei He ^a,^b and Hai-Bo Wang ^a ^*

^aCollege of Food Science and Light Industry, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, and ^bCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's People's Republic of China
^*Correspondence e-mail: wanghaibo@njut.edu.cn

(Received 6 September 2010; accepted 29 September 2010; online 9 October 2010)

In the crystal structure of the title compound, C₉H₉F₃O₃S, intermolecular C—H⋯O hydrogen bonds link the molecules along the c-axis direction. Also present are slipped π–π stacking interactions between phenylene rings, with perpendicular interplanar distances of 3.55 (2) Å and centroid–centroid distances of 3.851 (2) Å.

Related literature

The title compound is a reactive electrophile and a useful intermediate in organic synthesis. For general background and the synthesis, see: Gøgsig et al. (2008 ). For a similar structure, see: Asano et al. (2009 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₉F₃O₃S
M_r = 254.22
Monoclinic, P 2₁ /c
a = 8.3760 (17) Å
b = 11.827 (2) Å
c = 11.145 (2) Å
β = 94.54 (3)°
V = 1100.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 293 K
0.30 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.909, T_max = 0.968
2149 measured reflections
2005 independent reflections
1355 reflections with I > 2σ(I)
R_int = 0.012
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.172
S = 1.00
2005 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯O1ⁱ	0.97	2.51	3.225 (4)	131
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 ); 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: https://doi.org/10.1107/S1600536810038894/zl2306sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810038894/zl2306Isup2.hkl

checkCIF report

Comment top

Electrophilic reagents play an important role in the synthesis of organic compounds and are often used in the synthesis of organic intermediates. (Asano et al. 2009). The title compound, 2,2,2-trifluoroethyl 4-methylbenzenesulfonate, is a electrophilic vinylation reagent commonly used for the synthesis of compounds such as vinyl styrenes that in turn find use as valuable intermediates in the synthesis of fine chemicals and as precursors to functionalized polymers (Gøgsig et al., 2008).

We report here in the crystal structure of the title compound, 2,2,2-trifluoroethyl 4-methylbenzenesulfonate. In the molecule of the title compound (Fig. 1), bond lengths (Allen et al., 1987) and angles are within normal ranges. An intramolecular C-H···O hydrogen bond (Table 1) results in the formation of a five-membered ring (C4/C5/S/O3/H4A). In the crystal structure, the weak intermolecular C8-H8···O1 hydrogen bond connects the molecules along the direction of the c axis (Fig. 2). Also present are slipped π-π stacking interactions between phenylene rings with perpendicular interplanar distances of 3.55 (2) Å and centroid to centroid distances of 3.851 (2) Å (symmetry operator for the second molecule: -x, 2-y, -z).

Related literature top

The title compound is an important reactive electrophile and a useful intermediate in organic synthesis. For general background and the synthesis, see: Gøgsig et al. (2008). For a similar structure, see: Asano et al. (2009). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, 2,2,2-trifluoroethyl 4-methylbenzenesulfonate was prepared on a literature procedure (Gøgsig et al., 2008). 2,2,2-Trifluoroethanol (19.90 mmol) and triethylamine (71.70 mmol) were dissolved in dry dichloromethane (20.0 mL). The solution was cooled to 273K and tosyl chloride (24.9 mmol) was added. The reaction was stirred at 273K for 1 h before being allowed to warm to room temperature. Hereafter the reaction was stirred at room temperature overnight. The organic phase was washed with brine (2 × 50 mL) and dried over sodium sulfate. After concentration in vacuo the crude product was purified by flash cromatography on silica gel using pentane/dichloromethane (4:1) and pentane/dichloromethane (3:1) as the eluents. This afforded of the title compound (96 % yield) as a colorless solid. Crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.

Structure description top

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1989); 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 the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of 2,2,2-trifluoroethyl 4-methylbenzenesulfonate. Dashed lines indicate intermolecular C-H···O interactions.

2,2,2-Trifluoroethyl 4-methylbenzenesulfonate top

Crystal data top

C₉H₉F₃O₃S	F(000) = 520
M_r = 254.22	D_x = 1.534 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 312 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.3760 (17) Å	Cell parameters from 25 reflections
b = 11.827 (2) Å	θ = 9–13°
c = 11.145 (2) Å	µ = 0.33 mm⁻¹
β = 94.54 (3)°	T = 293 K
V = 1100.6 (4) Å³	Needle, colourless
Z = 4	0.30 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1355 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.012
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→14
T_min = 0.909, T_max = 0.968	l = −13→13
2149 measured reflections	3 standard reflections every 200 reflections
2005 independent reflections	intensity decay: 1%

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1P)² + 0.350P] where P = (F_o² + 2F_c²)/3
2005 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₉H₉F₃O₃S	V = 1100.6 (4) Å³
M_r = 254.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3760 (17) Å	µ = 0.33 mm⁻¹
b = 11.827 (2) Å	T = 293 K
c = 11.145 (2) Å	0.30 × 0.10 × 0.10 mm
β = 94.54 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1355 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.012
T_min = 0.909, T_max = 0.968	3 standard reflections every 200 reflections
2149 measured reflections	intensity decay: 1%
2005 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.00	Δρ_max = 0.21 e Å⁻³
2005 reflections	Δρ_min = −0.29 e Å⁻³
146 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	0.22668 (10)	0.81228 (8)	0.14051 (7)	0.0524 (3)
O1	0.2130 (3)	0.8490 (2)	0.2610 (2)	0.0726 (8)
O2	0.2305 (3)	0.6787 (2)	0.15228 (18)	0.0564 (7)
O3	0.3590 (3)	0.8450 (2)	0.0778 (2)	0.0685 (8)
C1	−0.3915 (5)	0.8728 (4)	−0.1679 (4)	0.0878 (14)
H1B	−0.3695	0.8862	−0.2499	0.132*
H1C	−0.4531	0.9345	−0.1399	0.132*
H1D	−0.4509	0.8038	−0.1630	0.132*
C2	−0.2361 (5)	0.8634 (3)	−0.0908 (3)	0.0590 (10)
C3	−0.0892 (5)	0.8731 (3)	−0.1392 (3)	0.0569 (9)
H3B	−0.0870	0.8893	−0.2207	0.068*
C4	0.0537 (4)	0.8594 (3)	−0.0705 (3)	0.0511 (8)
H4A	0.1509	0.8650	−0.1051	0.061*
C5	0.0493 (4)	0.8369 (3)	0.0522 (3)	0.0442 (8)
C6	−0.0958 (4)	0.8308 (3)	0.1034 (3)	0.0517 (9)
H6A	−0.0981	0.8178	0.1856	0.062*
C7	−0.2343 (5)	0.8439 (3)	0.0336 (3)	0.0623 (10)
H7A	−0.3310	0.8399	0.0690	0.075*
C8	0.2628 (5)	0.6142 (3)	0.0482 (3)	0.0662 (11)
H8A	0.3679	0.6333	0.0234	0.079*
H8B	0.1840	0.6316	−0.0178	0.079*
C9	0.2565 (6)	0.4960 (4)	0.0770 (4)	0.0717 (11)
F3	0.1153 (4)	0.4632 (3)	0.1101 (3)	0.1040 (9)
F2	0.3549 (4)	0.4617 (2)	0.1673 (3)	0.1064 (10)
F1	0.2812 (4)	0.4335 (3)	−0.0197 (3)	0.1119 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0482 (5)	0.0686 (6)	0.0399 (5)	0.0007 (4)	0.0000 (3)	−0.0052 (4)
O1	0.0794 (19)	0.095 (2)	0.0415 (14)	0.0052 (15)	−0.0036 (12)	−0.0168 (14)
O2	0.0625 (16)	0.0732 (17)	0.0339 (12)	0.0100 (12)	0.0057 (10)	0.0013 (11)
O3	0.0511 (15)	0.0831 (19)	0.0722 (17)	−0.0068 (13)	0.0115 (13)	0.0018 (15)
C1	0.075 (3)	0.096 (3)	0.087 (3)	0.005 (3)	−0.027 (2)	0.007 (3)
C2	0.063 (2)	0.056 (2)	0.055 (2)	0.0001 (18)	−0.0071 (18)	−0.0006 (18)
C3	0.070 (2)	0.070 (2)	0.0309 (17)	0.0066 (19)	0.0043 (16)	0.0094 (16)
C4	0.054 (2)	0.061 (2)	0.0397 (18)	0.0017 (16)	0.0090 (15)	0.0023 (16)
C5	0.0430 (18)	0.0482 (18)	0.0411 (17)	0.0026 (14)	0.0024 (13)	−0.0028 (14)
C6	0.051 (2)	0.063 (2)	0.0421 (18)	−0.0018 (16)	0.0120 (15)	0.0010 (16)
C7	0.052 (2)	0.069 (2)	0.066 (2)	−0.0010 (18)	0.0102 (18)	0.005 (2)
C8	0.079 (3)	0.070 (3)	0.052 (2)	0.007 (2)	0.0204 (19)	−0.0014 (19)
C9	0.079 (3)	0.068 (3)	0.067 (3)	−0.003 (2)	−0.005 (2)	−0.004 (2)
F3	0.096 (2)	0.110 (2)	0.106 (2)	−0.0209 (17)	0.0106 (16)	0.0062 (17)
F2	0.106 (2)	0.094 (2)	0.116 (2)	0.0091 (16)	−0.0117 (18)	0.0086 (17)
F1	0.132 (3)	0.096 (2)	0.109 (2)	0.0005 (18)	0.0163 (19)	−0.0149 (17)

Geometric parameters (Å, º) top

S—O3	1.410 (3)	C4—C5	1.397 (4)
S—O1	1.425 (2)	C4—H4A	0.9300
S—O2	1.585 (3)	C5—C6	1.385 (4)
S—C5	1.740 (3)	C6—C7	1.354 (5)
O2—C8	1.432 (4)	C6—H6A	0.9300
C1—C2	1.506 (5)	C7—H7A	0.9300
C1—H1B	0.9600	C8—C9	1.437 (6)
C1—H1C	0.9600	C8—H8A	0.9700
C1—H1D	0.9600	C8—H8B	0.9700
C2—C3	1.387 (5)	C9—F2	1.314 (5)
C2—C7	1.404 (5)	C9—F3	1.325 (5)
C3—C4	1.379 (5)	C9—F1	1.336 (5)
C3—H3B	0.9300

O3—S—O1	120.54 (18)	C6—C5—C4	120.4 (3)
O3—S—O2	107.64 (15)	C6—C5—S	119.7 (2)
O1—S—O2	103.21 (15)	C4—C5—S	119.9 (3)
O3—S—C5	110.08 (16)	C7—C6—C5	119.8 (3)
O1—S—C5	110.68 (16)	C7—C6—H6A	120.1
O2—S—C5	102.95 (15)	C5—C6—H6A	120.1
C8—O2—S	117.9 (2)	C6—C7—C2	121.9 (3)
C2—C1—H1B	109.5	C6—C7—H7A	119.1
C2—C1—H1C	109.5	C2—C7—H7A	119.1
H1B—C1—H1C	109.5	O2—C8—C9	109.0 (3)
C2—C1—H1D	109.5	O2—C8—H8A	109.9
H1B—C1—H1D	109.5	C9—C8—H8A	109.9
H1C—C1—H1D	109.5	O2—C8—H8B	109.9
C3—C2—C7	117.2 (3)	C9—C8—H8B	109.9
C3—C2—C1	121.7 (4)	H8A—C8—H8B	108.3
C7—C2—C1	121.1 (4)	F2—C9—F3	102.5 (4)
C4—C3—C2	122.1 (3)	F2—C9—F1	108.7 (4)
C4—C3—H3B	118.9	F3—C9—F1	105.1 (4)
C2—C3—H3B	118.9	F2—C9—C8	116.1 (4)
C3—C4—C5	118.5 (3)	F3—C9—C8	113.4 (4)
C3—C4—H4A	120.7	F1—C9—C8	110.4 (4)
C5—C4—H4A	120.7

O3—S—O2—C8	−44.3 (3)	O1—S—C5—C4	149.6 (3)
O1—S—O2—C8	−172.8 (3)	O2—S—C5—C4	−100.7 (3)
C5—S—O2—C8	72.0 (3)	C4—C5—C6—C7	1.7 (5)
C7—C2—C3—C4	2.8 (6)	S—C5—C6—C7	−176.5 (3)
C1—C2—C3—C4	−176.9 (4)	C5—C6—C7—C2	0.2 (6)
C2—C3—C4—C5	−1.1 (6)	C3—C2—C7—C6	−2.4 (6)
C3—C4—C5—C6	−1.2 (5)	C1—C2—C7—C6	177.4 (4)
C3—C4—C5—S	176.9 (3)	S—O2—C8—C9	−178.5 (3)
O3—S—C5—C6	−168.1 (3)	O2—C8—C9—F2	−57.8 (5)
O1—S—C5—C6	−32.3 (3)	O2—C8—C9—F3	60.4 (5)
O2—S—C5—C6	77.4 (3)	O2—C8—C9—F1	178.0 (3)
O3—S—C5—C4	13.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O3	0.93	2.59	2.938 (4)	103
C8—H8B···O1ⁱ	0.97	2.51	3.225 (4)	131

Symmetry code: (i) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₉H₉F₃O₃S
M_r	254.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.3760 (17), 11.827 (2), 11.145 (2)
β (°)	94.54 (3)
V (Å³)	1100.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.909, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	2149, 2005, 1355
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.172, 1.00
No. of reflections	2005
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.29

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1989), 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
C4—H4A···O3	0.9300	2.5900	2.938 (4)	103.00
C8—H8B···O1ⁱ	0.9700	2.5100	3.225 (4)	131.00

Symmetry code: (i) x, −y+3/2, z−1/2.

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
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Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
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Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2779

https://doi.org/10.1107/S1600536810038894

Open

access