organic compounds
3,5-Bis(trifluoromethyl)phenyl 4-methylbenzenesulfonate
aFaculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland
*Correspondence e-mail: bzarychta@uni.opole.pl
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 . 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)°.
of the title compound, there is one independent molecule. The molecular structure is shown in Fig. 1In 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].
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 was obtained. The solution was warmed, then left to stand in refrigerator (−20°C).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1560197
https://doi.org/10.1107/S2414314617009816/bt4055sup1.cif
contains datablocks I, global. DOI: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
Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell
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).C15H10F6O3S | Z = 2 |
Mr = 384.29 | F(000) = 388 |
Triclinic, P1 | Dx = 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 |
Oxford Diffraction Xcalibur diffractometer | 2614 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.013 |
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm-1 | θmax = 26.0°, θmin = 3.5° |
ω–scan | h = −10→10 |
5437 measured reflections | k = −6→10 |
3070 independent reflections | l = −15→15 |
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(Fo2) + (0.0445P)2 + 0.1137P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.002 |
3070 reflections | Δρmax = 0.27 e Å−3 |
254 parameters | Δρmin = −0.37 e Å−3 |
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 CAr—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) and with Cmethyl—H = 0.96 Å and Uiso(H) = 1.5Ueq(C). |
x | y | z | Uiso*/Ueq | 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) |
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) |
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) |
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
Ackermann, L., Althammer, A. & Born, R. (2006). Angew. Chem. Int. Ed. 45, 2619–2622. Web of Science CrossRef CAS Google Scholar
Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Murai, N., Miyano, M., Yonaga, M. & Tanaka, K. (2012). Org. Lett. 14, 2818–2821. Web of Science CrossRef CAS PubMed Google Scholar
Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Torborg, C. & Beller, M. (2009). Adv. Synth. Catal. 351, 3027–3043. Web of Science CrossRef CAS Google Scholar
Zhou, J. & Fu, G. C. (2003). J. Am. Chem. Soc. 125, 12527–12530. Web of Science CrossRef PubMed CAS Google Scholar
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