3,5-Bis(tri­fluoro­meth­yl)phenyl 4-methyl­benzene­sulfonate

Olszowy, A.; Siodłak, D.; Zarychta, B.

doi:10.1107/S2414314617009816

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 7| July 2017| x170981

https://doi.org/10.1107/S2414314617009816

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3,5-Bis(trifluoromethyl)phenyl 4-methylbenzenesulfonate

Aleksandra Olszowy,^a Dawid Siodłak ^a and Bartosz Zarychta ^a ^*

^aFaculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland
^*Correspondence e-mail: bzarychta@uni.opole.pl

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 30 June 2017; accepted 3 July 2017; online 7 July 2017)

Molecules of the title compound, C₁₅H₁₀F₆O₃S, are composed of 3,5-bis(trifluoromethyl)phenyl substituted with a toluene-4-sulfonate group. The dihedral angle between two aromatic moieties is 45.10 (5)°. In the crystal, molecules are connected by weak C—H⋯O and C—H⋯F contacts. One of the trifluoromethyl groups is disordered.

Keywords: crystal structure; tosylates; cross-coupling reactions.

CCDC reference: 1560197

Structure description

Transition-metal-catalyzed cross-coupling reactions can be applied to aryl tosylates (Ackermann et al., 2006 ; Zhou & Fu, 2003 ). We apply 4-methylbenzenesulfonates to study the reaction progress and performance using first-row metal catalysts. The high natural abundance of these non-precious transition metal elements makes them an interesting target of study (Torborg & Beller, 2009 ).

In the asymmetric unit of the title compound, there is one independent molecule. The molecular structure is shown in Fig. 1. In the molecular structure, the bond lengths and angles are within normal ranges (Allen et al., 2002 ). One of the trifluoromethyl groups in the molecule is disordered with occupation factors of 0.65 and 0.35. The dihedral angle between the aromatic moieties is 45.10 (5)°.

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

In the crystal (Fig. 2), there are two hydrogen bonds (Table 1), both of which connect the molecules into dimers. There are also two F⋯π T-shape halogen bonds to a 3,5-di(trifluoromethyl)phenyl moiety. The distances of F5Aⁱ and F5Bⁱ from the centre of a plane defined by atoms C9–C13 of the 3,5-di(trifluoromethyl)phenyl ring are 3.348 (12) and 3.256 (19) Å [symmetry code: (i) −x, −y + 1, −z + 1].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯F4Aⁱ	0.93	2.55	3.308 (3)	139
C9—H9⋯O1ⁱⁱ	0.93	2.40	3.2959 (17)	162
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y, -z.

Figure 2
The crystal packing of the title compound, viewed along the a axis. Disordered fluorine atoms have been omited for clarity. Hydrogen bonds are shown as dashed lines

Synthesis and crystallization

3,5-Di(trifluoromethyl)phenyl 4-methylbenzenesulfonate was synthesized according to a procedure described by Murai and co-workers (Murai et al., 2012 ). The crystallization was performed in a diethyl ether solution. Diethyl ether (0.6 ml) was placed in storage reaction vials (8 ml) with silicone septa. The title compound was placed in small portions until a saturated solution was obtained. The solution was warmed, then left to stand in refrigerator (−20°C).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₀F₆O₃S
M_r	384.29
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	8.2805 (3), 8.6053 (3), 12.2396 (4)
α, β, γ (°)	103.519 (3), 99.935 (3), 105.188 (3)
V (Å³)	792.56 (5)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.28
Crystal size (mm)	0.4 × 0.25 × 0.24

Data collection
Diffractometer	Oxford Diffraction Xcalibur
No. of measured, independent and observed [I > 2σ(I)] reflections	5437, 3070, 2614
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.080, 1.06
No. of reflections	3070
No. of parameters	254
No. of restraints	36
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.37
Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), SHELXS2014 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and SHELXTL (Sheldrick, 2008).

Structural data

CCDC reference: 1560197

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617009816/bt4055sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617009816/bt4055Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617009816/bt4055Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

3,5-Bis(trifluoromethyl)phenyl 4-methylbenzenesulfonate top

Crystal data top

C₁₅H₁₀F₆O₃S	Z = 2
M_r = 384.29	F(000) = 388
Triclinic, P1	D_x = 1.610 Mg m⁻³
a = 8.2805 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.6053 (3) Å	Cell parameters from 5437 reflections
c = 12.2396 (4) Å	θ = 3.5–26.0°
α = 103.519 (3)°	µ = 0.28 mm⁻¹
β = 99.935 (3)°	T = 100 K
γ = 105.188 (3)°	Irregular, colourless
V = 792.56 (5) Å³	0.4 × 0.25 × 0.24 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer	2614 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.013
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	θ_max = 26.0°, θ_min = 3.5°
ω–scan	h = −10→10
5437 measured reflections	k = −6→10
3070 independent reflections	l = −15→15

Refinement top

Refinement on F²	36 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0445P)² + 0.1137P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
3070 reflections	Δρ_max = 0.27 e Å⁻³
254 parameters	Δρ_min = −0.37 e Å⁻³

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. All H atoms were found in a difference map but set to idealized positions and treated as riding with C_Ar—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) and with C_methyl—H = 0.96 Å and U_iso(H) = 1.5U_eq(C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.18701 (5)	0.27629 (4)	0.03515 (3)	0.01913 (11)
O1	0.07383 (14)	0.23781 (13)	−0.07602 (9)	0.0260 (3)
O2	0.28474 (14)	0.16929 (13)	0.05977 (9)	0.0253 (3)
O3	0.05670 (13)	0.27937 (12)	0.11983 (8)	0.0194 (2)
F1	0.27606 (16)	−0.09183 (13)	0.34224 (9)	0.0447 (3)
F2	0.03104 (14)	−0.12166 (12)	0.38253 (10)	0.0457 (3)
F3	0.26421 (14)	0.01544 (11)	0.51597 (8)	0.0371 (3)
F4A	0.3770 (3)	0.6057 (3)	0.62880 (19)	0.0405 (6)	0.65
F5A	0.1573 (14)	0.6652 (12)	0.5462 (8)	0.0432 (17)	0.65
F6A	0.3974 (7)	0.7323 (6)	0.4990 (3)	0.0254 (6)	0.65
F5B	0.134 (2)	0.669 (2)	0.5219 (14)	0.0266 (17)	0.35
F4B	0.2762 (7)	0.5775 (6)	0.6351 (4)	0.0582 (13)	0.35
F6B	0.3987 (15)	0.7169 (12)	0.5299 (7)	0.055 (2)	0.35
C1	0.32014 (19)	0.48591 (18)	0.07914 (12)	0.0179 (3)
C2	0.48144 (19)	0.53300 (19)	0.15499 (13)	0.0215 (3)
H2	0.5222	0.4533	0.1802	0.026*
C3	0.5807 (2)	0.7017 (2)	0.19247 (13)	0.0246 (3)
H3	0.6894	0.7346	0.2429	0.030*
C4	0.5209 (2)	0.82248 (19)	0.15611 (13)	0.0234 (3)
C5	0.3587 (2)	0.77115 (19)	0.07913 (14)	0.0242 (3)
H5	0.3177	0.8507	0.0538	0.029*
C6	0.2580 (2)	0.60379 (19)	0.03999 (13)	0.0216 (3)
H6	0.1503	0.5704	−0.0117	0.026*
C7	0.6294 (2)	1.0054 (2)	0.19699 (15)	0.0336 (4)
H7A	0.6946	1.0293	0.1418	0.050*
H7B	0.7071	1.0288	0.2710	0.050*
H7C	0.5556	1.0747	0.2042	0.050*
C8	0.12143 (18)	0.28625 (18)	0.23573 (12)	0.0172 (3)
C9	0.12658 (18)	0.13922 (17)	0.26128 (13)	0.0183 (3)
H9	0.0925	0.0376	0.2028	0.022*
C10	0.18379 (19)	0.14705 (18)	0.37620 (13)	0.0183 (3)
C11	0.23417 (19)	0.29824 (18)	0.46388 (13)	0.0193 (3)
H11	0.2714	0.3021	0.5409	0.023*
C12	0.22819 (19)	0.44313 (18)	0.43511 (13)	0.0212 (3)
C13	0.17096 (19)	0.43894 (18)	0.32017 (13)	0.0196 (3)
H13	0.1663	0.5364	0.3010	0.024*
C14	0.1894 (2)	−0.01242 (19)	0.40458 (14)	0.0247 (3)
C15	0.2802 (3)	0.6082 (2)	0.52824 (14)	0.0308 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0247 (2)	0.01547 (19)	0.01623 (19)	0.00521 (15)	0.00510 (15)	0.00420 (14)
O1	0.0326 (6)	0.0220 (6)	0.0168 (5)	0.0023 (5)	0.0022 (5)	0.0034 (4)
O2	0.0344 (6)	0.0198 (5)	0.0274 (6)	0.0126 (5)	0.0131 (5)	0.0088 (5)
O3	0.0201 (5)	0.0210 (5)	0.0170 (5)	0.0058 (4)	0.0030 (4)	0.0070 (4)
F1	0.0808 (9)	0.0347 (6)	0.0450 (7)	0.0411 (6)	0.0343 (6)	0.0212 (5)
F2	0.0434 (6)	0.0265 (5)	0.0610 (8)	−0.0035 (5)	0.0023 (5)	0.0253 (5)
F3	0.0649 (7)	0.0238 (5)	0.0235 (5)	0.0183 (5)	0.0016 (5)	0.0105 (4)
F4A	0.0712 (15)	0.0204 (9)	0.0191 (9)	0.0125 (11)	−0.0070 (11)	0.0012 (7)
F5A	0.038 (3)	0.027 (2)	0.056 (4)	0.0084 (15)	0.022 (3)	−0.008 (2)
F6A	0.0257 (11)	0.0137 (9)	0.0306 (14)	0.0016 (8)	0.0007 (11)	0.0049 (10)
F5B	0.034 (4)	0.011 (2)	0.039 (4)	0.012 (2)	0.017 (3)	0.006 (3)
F4B	0.116 (4)	0.033 (2)	0.0211 (18)	0.039 (3)	−0.005 (3)	−0.0005 (15)
F6B	0.032 (3)	0.037 (4)	0.070 (5)	0.004 (3)	0.009 (4)	−0.023 (3)
C1	0.0217 (7)	0.0169 (7)	0.0149 (7)	0.0049 (6)	0.0063 (6)	0.0042 (6)
C2	0.0247 (8)	0.0249 (8)	0.0169 (7)	0.0095 (7)	0.0054 (6)	0.0077 (6)
C3	0.0227 (8)	0.0302 (8)	0.0152 (7)	0.0036 (7)	0.0027 (6)	0.0027 (6)
C4	0.0279 (8)	0.0203 (8)	0.0187 (8)	0.0031 (7)	0.0113 (6)	0.0007 (6)
C5	0.0280 (8)	0.0200 (8)	0.0286 (9)	0.0102 (7)	0.0108 (7)	0.0092 (7)
C6	0.0213 (8)	0.0217 (8)	0.0221 (8)	0.0070 (6)	0.0043 (6)	0.0076 (6)
C7	0.0381 (10)	0.0219 (8)	0.0314 (10)	0.0005 (7)	0.0106 (8)	−0.0008 (7)
C8	0.0147 (7)	0.0199 (7)	0.0176 (7)	0.0048 (6)	0.0047 (6)	0.0066 (6)
C9	0.0188 (7)	0.0140 (7)	0.0195 (7)	0.0026 (6)	0.0050 (6)	0.0028 (6)
C10	0.0193 (7)	0.0162 (7)	0.0213 (8)	0.0059 (6)	0.0074 (6)	0.0071 (6)
C11	0.0225 (8)	0.0195 (7)	0.0166 (7)	0.0081 (6)	0.0050 (6)	0.0051 (6)
C12	0.0248 (8)	0.0177 (7)	0.0213 (8)	0.0088 (6)	0.0056 (6)	0.0039 (6)
C13	0.0220 (7)	0.0153 (7)	0.0235 (8)	0.0072 (6)	0.0058 (6)	0.0075 (6)
C14	0.0346 (9)	0.0183 (7)	0.0221 (8)	0.0086 (7)	0.0076 (7)	0.0072 (6)
C15	0.0468 (11)	0.0209 (9)	0.0233 (9)	0.0151 (9)	0.0010 (8)	0.0042 (7)

Geometric parameters (Å, º) top

S1—O1	1.4234 (11)	C4—C5	1.395 (2)
S1—O2	1.4246 (11)	C4—C7	1.507 (2)
S1—O3	1.6208 (11)	C5—C6	1.382 (2)
S1—C1	1.7488 (15)	C5—H5	0.9300
O3—C8	1.4089 (17)	C6—H6	0.9300
F1—C14	1.3293 (19)	C7—H7A	0.9600
F2—C14	1.3374 (19)	C7—H7B	0.9600
F3—C14	1.3334 (18)	C7—H7C	0.9600
F4A—C15	1.356 (3)	C8—C13	1.378 (2)
F5A—C15	1.270 (11)	C8—C9	1.382 (2)
F6A—C15	1.402 (5)	C9—C10	1.384 (2)
F5B—C15	1.432 (19)	C9—H9	0.9300
F4B—C15	1.398 (5)	C10—C11	1.388 (2)
F6B—C15	1.158 (10)	C10—C14	1.502 (2)
C1—C2	1.387 (2)	C11—C12	1.383 (2)
C1—C6	1.393 (2)	C11—H11	0.9300
C2—C3	1.388 (2)	C12—C13	1.394 (2)
C2—H2	0.9300	C12—C15	1.502 (2)
C3—C4	1.391 (2)	C13—H13	0.9300
C3—H3	0.9300

O1—S1—O2	121.19 (7)	C8—C9—C10	118.28 (13)
O1—S1—O3	102.31 (6)	C8—C9—H9	120.9
O2—S1—O3	108.14 (6)	C10—C9—H9	120.9
O1—S1—C1	110.29 (7)	C9—C10—C11	121.09 (13)
O2—S1—C1	110.36 (7)	C9—C10—C14	118.55 (13)
O3—S1—C1	102.61 (6)	C11—C10—C14	120.37 (13)
C8—O3—S1	117.42 (9)	C12—C11—C10	119.08 (14)
C2—C1—C6	121.31 (14)	C12—C11—H11	120.5
C2—C1—S1	119.98 (12)	C10—C11—H11	120.5
C6—C1—S1	118.66 (11)	C11—C12—C13	121.06 (14)
C1—C2—C3	118.59 (14)	C11—C12—C15	120.26 (14)
C1—C2—H2	120.7	C13—C12—C15	118.67 (13)
C3—C2—H2	120.7	C8—C13—C12	118.07 (13)
C2—C3—C4	121.34 (14)	C8—C13—H13	121.0
C2—C3—H3	119.3	C12—C13—H13	121.0
C4—C3—H3	119.3	F1—C14—F3	107.05 (13)
C3—C4—C5	118.76 (14)	F1—C14—F2	106.36 (13)
C3—C4—C7	121.10 (15)	F3—C14—F2	106.91 (12)
C5—C4—C7	120.14 (15)	F1—C14—C10	111.94 (13)
C6—C5—C4	120.95 (15)	F3—C14—C10	112.39 (13)
C6—C5—H5	119.5	F2—C14—C10	111.81 (13)
C4—C5—H5	119.5	F5A—C15—F4A	111.0 (4)
C5—C6—C1	119.04 (14)	F6B—C15—F4B	114.9 (5)
C5—C6—H6	120.5	F5A—C15—F6A	106.2 (5)
C1—C6—H6	120.5	F4A—C15—F6A	101.2 (2)
C4—C7—H7A	109.5	F6B—C15—F5B	107.7 (8)
C4—C7—H7B	109.5	F4B—C15—F5B	94.9 (7)
H7A—C7—H7B	109.5	F6B—C15—C12	119.4 (5)
C4—C7—H7C	109.5	F5A—C15—C12	115.2 (5)
H7A—C7—H7C	109.5	F4A—C15—C12	112.22 (16)
H7B—C7—H7C	109.5	F4B—C15—C12	109.2 (2)
C13—C8—C9	122.41 (13)	F6A—C15—C12	109.9 (2)
C13—C8—O3	118.51 (12)	F5B—C15—C12	107.7 (7)
C9—C8—O3	119.03 (12)

O1—S1—O3—C8	169.55 (10)	C14—C10—C11—C12	179.80 (14)
O2—S1—O3—C8	40.56 (11)	C10—C11—C12—C13	0.7 (2)
C1—S1—O3—C8	−76.08 (11)	C10—C11—C12—C15	179.37 (15)
O1—S1—C1—C2	−152.88 (12)	C9—C8—C13—C12	0.1 (2)
O2—S1—C1—C2	−16.32 (15)	O3—C8—C13—C12	177.43 (12)
O3—S1—C1—C2	98.72 (13)	C11—C12—C13—C8	−0.4 (2)
O1—S1—C1—C6	29.51 (14)	C15—C12—C13—C8	−179.14 (15)
O2—S1—C1—C6	166.07 (11)	C9—C10—C14—F1	52.61 (19)
O3—S1—C1—C6	−78.89 (12)	C11—C10—C14—F1	−127.77 (16)
C6—C1—C2—C3	0.5 (2)	C9—C10—C14—F3	173.13 (13)
S1—C1—C2—C3	−177.05 (11)	C11—C10—C14—F3	−7.2 (2)
C1—C2—C3—C4	0.4 (2)	C9—C10—C14—F2	−66.61 (18)
C2—C3—C4—C5	−0.9 (2)	C11—C10—C14—F2	113.01 (16)
C2—C3—C4—C7	−179.91 (14)	C11—C12—C15—F6B	116.5 (6)
C3—C4—C5—C6	0.5 (2)	C13—C12—C15—F6B	−64.8 (6)
C7—C4—C5—C6	179.48 (14)	C11—C12—C15—F5A	−109.7 (5)
C4—C5—C6—C1	0.4 (2)	C13—C12—C15—F5A	69.1 (5)
C2—C1—C6—C5	−0.9 (2)	C11—C12—C15—F4A	18.7 (3)
S1—C1—C6—C5	176.65 (12)	C13—C12—C15—F4A	−162.53 (17)
S1—O3—C8—C13	101.10 (13)	C11—C12—C15—F4B	−18.6 (3)
S1—O3—C8—C9	−81.44 (14)	C13—C12—C15—F4B	160.1 (3)
C13—C8—C9—C10	0.0 (2)	C11—C12—C15—F6A	130.5 (3)
O3—C8—C9—C10	−177.35 (12)	C13—C12—C15—F6A	−50.8 (3)
C8—C9—C10—C11	0.3 (2)	C11—C12—C15—F5B	−120.5 (7)
C8—C9—C10—C14	179.88 (13)	C13—C12—C15—F5B	58.2 (7)
C9—C10—C11—C12	−0.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···F4Aⁱ	0.93	2.55	3.308 (3)	139
C9—H9···O1ⁱⁱ	0.93	2.40	3.2959 (17)	162

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

Funding information

Funding for this research was provided by: Narodowe Centrum Nauki (grant No. 2014/15/D/ST5/02731).

References

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