organic compounds
Biphenyl-4-yl 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, C19H16O3S, are composed of a biphenyl moiety substituted with a toluene-4-sulfonate group. The dihedral angle between the two coplanar biphenyl rings and the toluene ring is 52.72 (6)°.
Keywords: crystal structure; tosylates; cross-coupling reactions.
CCDC reference: 1560198
Structure description
Aryl tosylates are important substrates in organic synthesis (Hugo et al., 2014; Xu & Zhang, 2011). Recently, the first-row metal catalysts became promising alternatives when used in cross-coupling reactions (Torborg & Beller, 2009). Aryl tosylates seem to be suitable substrates for this type of reaction (So et al., 2008; Zim et al. 2001).
In the . In the molecular structure the bond lengths and angles are within normal ranges (Allen et al., 2002). The dihedral angle between the two coplanar biphenyl rings and the toluene ring is 52.72 (6)°. The crystal packing is shown in Fig. 2.
of the title compound, there is one independent molecule. The crystal is twinned by inversion. The molecular structure is shown in Fig. 1Synthesis and crystallization
Biphenyl-4-yl 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 added in small portions until a was obtained. The solution was warmed, and then, it was left to stand in a refrigerator (−20°C).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 1Structural data
CCDC reference: 1560198
https://doi.org/10.1107/S2414314617009828/bt4056sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617009828/bt4056Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617009828/bt4056Isup3.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).C19H16O3S | Dx = 1.410 Mg m−3 |
Mr = 324.38 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pca21 | Cell parameters from 9829 reflections |
a = 33.2932 (10) Å | θ = 3.2–26.0° |
b = 7.9284 (2) Å | µ = 0.23 mm−1 |
c = 5.7903 (2) Å | T = 100 K |
V = 1528.42 (8) Å3 | Irregular, colourless |
Z = 4 | 0.3 × 0.25 × 0.12 mm |
F(000) = 680 |
Oxford Diffraction Xcalibur diffractometer | 1978 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm-1 | θmax = 26.0°, θmin = 3.2° |
ω–scan | h = −41→40 |
9829 measured reflections | k = −9→9 |
2222 independent reflections | l = −4→7 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.026 | w = 1/[σ2(Fo2) + (0.0347P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.057 | (Δ/σ)max < 0.001 |
S = 0.98 | Δρmax = 0.15 e Å−3 |
2222 reflections | Δρmin = −0.27 e Å−3 |
210 parameters | Absolute structure: Refined as an inversion twin. |
1 restraint | Absolute structure parameter: 0.32 (11) |
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. Refined as a 2-component inversion twin. All H atoms were found in a difference map but set to idealized positions and treated as riding with Caromatic—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 | ||
S1 | 0.32398 (2) | 0.10318 (6) | −0.15317 (14) | 0.01524 (13) | |
O1 | 0.33997 (5) | 0.14325 (19) | −0.3745 (3) | 0.0215 (4) | |
O2 | 0.29105 (4) | −0.00997 (18) | −0.1300 (3) | 0.0226 (4) | |
O3 | 0.35856 (4) | 0.01401 (17) | −0.0021 (3) | 0.0166 (3) | |
C1 | 0.31403 (6) | 0.2901 (3) | −0.0019 (4) | 0.0138 (4) | |
C2 | 0.29338 (6) | 0.2828 (3) | 0.2065 (4) | 0.0156 (5) | |
H2 | 0.2843 | 0.1803 | 0.2644 | 0.019* | |
C3 | 0.28667 (6) | 0.4316 (2) | 0.3261 (4) | 0.0177 (4) | |
H3 | 0.2730 | 0.4282 | 0.4661 | 0.021* | |
C4 | 0.30000 (6) | 0.5864 (3) | 0.2409 (4) | 0.0169 (5) | |
C5 | 0.31986 (6) | 0.5899 (3) | 0.0296 (4) | 0.0176 (5) | |
H5 | 0.3283 | 0.6925 | −0.0309 | 0.021* | |
C6 | 0.32716 (6) | 0.4425 (3) | −0.0919 (4) | 0.0164 (5) | |
H6 | 0.3407 | 0.4457 | −0.2322 | 0.020* | |
C7 | 0.29299 (6) | 0.7459 (3) | 0.3755 (5) | 0.0238 (5) | |
H7A | 0.3169 | 0.8135 | 0.3732 | 0.036* | |
H7B | 0.2863 | 0.7182 | 0.5323 | 0.036* | |
H7C | 0.2713 | 0.8079 | 0.3070 | 0.036* | |
C8 | 0.39783 (6) | 0.0843 (2) | −0.0111 (4) | 0.0159 (5) | |
C9 | 0.42271 (6) | 0.0434 (3) | −0.1928 (4) | 0.0208 (5) | |
H9 | 0.4137 | −0.0252 | −0.3122 | 0.025* | |
C10 | 0.46155 (6) | 0.1068 (3) | −0.1938 (4) | 0.0209 (5) | |
H10 | 0.4785 | 0.0803 | −0.3163 | 0.025* | |
C11 | 0.47596 (6) | 0.2096 (3) | −0.0158 (4) | 0.0152 (4) | |
C12 | 0.44964 (6) | 0.2455 (3) | 0.1645 (4) | 0.0213 (5) | |
H12 | 0.4585 | 0.3126 | 0.2860 | 0.026* | |
C13 | 0.41057 (7) | 0.1839 (3) | 0.1682 (4) | 0.0205 (5) | |
H13 | 0.3934 | 0.2097 | 0.2899 | 0.025* | |
C14 | 0.51792 (6) | 0.2769 (2) | −0.0208 (4) | 0.0149 (4) | |
C15 | 0.54399 (7) | 0.2397 (3) | −0.2010 (4) | 0.0271 (6) | |
H15 | 0.5351 | 0.1713 | −0.3210 | 0.032* | |
C16 | 0.58282 (7) | 0.3019 (3) | −0.2067 (4) | 0.0276 (6) | |
H16 | 0.5996 | 0.2747 | −0.3296 | 0.033* | |
C17 | 0.59683 (7) | 0.4040 (3) | −0.0314 (4) | 0.0223 (5) | |
H17 | 0.6229 | 0.4464 | −0.0355 | 0.027* | |
C18 | 0.57163 (7) | 0.4421 (3) | 0.1493 (5) | 0.0276 (6) | |
H18 | 0.5807 | 0.5107 | 0.2686 | 0.033* | |
C19 | 0.53276 (7) | 0.3792 (3) | 0.1556 (5) | 0.0248 (5) | |
H19 | 0.5163 | 0.4058 | 0.2799 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0146 (2) | 0.0136 (2) | 0.0175 (2) | 0.0014 (2) | −0.0020 (2) | −0.0023 (3) |
O1 | 0.0248 (8) | 0.0230 (8) | 0.0168 (8) | 0.0061 (7) | −0.0012 (7) | −0.0020 (7) |
O2 | 0.0182 (8) | 0.0168 (7) | 0.0329 (9) | −0.0020 (6) | −0.0032 (8) | −0.0050 (8) |
O3 | 0.0140 (7) | 0.0130 (7) | 0.0229 (8) | −0.0004 (6) | −0.0009 (7) | 0.0024 (7) |
C1 | 0.0125 (10) | 0.0122 (10) | 0.0167 (11) | 0.0017 (8) | −0.0039 (9) | −0.0024 (9) |
C2 | 0.0154 (11) | 0.0155 (11) | 0.0158 (12) | 0.0008 (8) | −0.0010 (9) | 0.0017 (9) |
C3 | 0.0141 (9) | 0.0223 (11) | 0.0167 (11) | 0.0017 (8) | −0.0002 (10) | 0.0004 (11) |
C4 | 0.0145 (11) | 0.0172 (11) | 0.0190 (11) | 0.0018 (9) | −0.0041 (9) | −0.0021 (10) |
C5 | 0.0164 (10) | 0.0139 (10) | 0.0223 (13) | −0.0038 (9) | −0.0016 (10) | 0.0036 (10) |
C6 | 0.0150 (10) | 0.0170 (11) | 0.0173 (13) | −0.0012 (8) | 0.0021 (9) | 0.0019 (8) |
C7 | 0.0240 (11) | 0.0199 (11) | 0.0274 (13) | 0.0034 (8) | −0.0014 (11) | −0.0060 (11) |
C8 | 0.0136 (10) | 0.0116 (10) | 0.0224 (12) | −0.0006 (8) | −0.0013 (9) | 0.0034 (10) |
C9 | 0.0197 (11) | 0.0207 (11) | 0.0221 (15) | 0.0010 (9) | −0.0021 (10) | −0.0077 (10) |
C10 | 0.0178 (10) | 0.0245 (11) | 0.0204 (15) | 0.0040 (9) | 0.0034 (10) | −0.0078 (10) |
C11 | 0.0167 (10) | 0.0113 (10) | 0.0176 (11) | 0.0037 (8) | −0.0015 (9) | 0.0023 (9) |
C12 | 0.0206 (11) | 0.0266 (12) | 0.0167 (12) | −0.0032 (10) | 0.0004 (10) | −0.0070 (10) |
C13 | 0.0192 (11) | 0.0259 (12) | 0.0162 (12) | 0.0003 (10) | 0.0039 (10) | −0.0038 (11) |
C14 | 0.0169 (10) | 0.0118 (10) | 0.0161 (11) | 0.0032 (8) | −0.0022 (9) | 0.0020 (9) |
C15 | 0.0256 (12) | 0.0318 (13) | 0.0239 (15) | −0.0073 (10) | 0.0033 (11) | −0.0126 (10) |
C16 | 0.0243 (12) | 0.0334 (13) | 0.0251 (15) | −0.0056 (10) | 0.0100 (10) | −0.0119 (12) |
C17 | 0.0165 (11) | 0.0244 (12) | 0.0261 (13) | −0.0021 (9) | −0.0003 (10) | −0.0007 (11) |
C18 | 0.0230 (12) | 0.0353 (14) | 0.0244 (13) | −0.0066 (11) | 0.0007 (11) | −0.0118 (12) |
C19 | 0.0193 (12) | 0.0349 (14) | 0.0201 (12) | −0.0025 (10) | 0.0031 (11) | −0.0094 (12) |
S1—O2 | 1.4228 (14) | C9—C10 | 1.388 (3) |
S1—O1 | 1.4238 (18) | C9—H9 | 0.9300 |
S1—O3 | 1.6095 (16) | C10—C11 | 1.399 (3) |
S1—C1 | 1.753 (2) | C10—H10 | 0.9300 |
O3—C8 | 1.422 (2) | C11—C12 | 1.392 (3) |
C1—C6 | 1.386 (3) | C11—C14 | 1.496 (3) |
C1—C2 | 1.390 (3) | C12—C13 | 1.389 (3) |
C2—C3 | 1.386 (3) | C12—H12 | 0.9300 |
C2—H2 | 0.9300 | C13—H13 | 0.9300 |
C3—C4 | 1.395 (3) | C14—C15 | 1.388 (3) |
C3—H3 | 0.9300 | C14—C19 | 1.395 (3) |
C4—C5 | 1.391 (3) | C15—C16 | 1.384 (3) |
C4—C7 | 1.504 (3) | C15—H15 | 0.9300 |
C5—C6 | 1.386 (3) | C16—C17 | 1.379 (3) |
C5—H5 | 0.9300 | C16—H16 | 0.9300 |
C6—H6 | 0.9300 | C17—C18 | 1.375 (3) |
C7—H7A | 0.9600 | C17—H17 | 0.9300 |
C7—H7B | 0.9600 | C18—C19 | 1.387 (3) |
C7—H7C | 0.9600 | C18—H18 | 0.9300 |
C8—C13 | 1.372 (3) | C19—H19 | 0.9300 |
C8—C9 | 1.378 (3) | ||
O2—S1—O1 | 120.90 (12) | C8—C9—C10 | 118.6 (2) |
O2—S1—O3 | 102.89 (9) | C8—C9—H9 | 120.7 |
O1—S1—O3 | 108.64 (9) | C10—C9—H9 | 120.7 |
O2—S1—C1 | 109.91 (10) | C9—C10—C11 | 121.8 (2) |
O1—S1—C1 | 109.37 (10) | C9—C10—H10 | 119.1 |
O3—S1—C1 | 103.59 (10) | C11—C10—H10 | 119.1 |
C8—O3—S1 | 117.76 (13) | C12—C11—C10 | 117.11 (19) |
C6—C1—C2 | 121.25 (19) | C12—C11—C14 | 121.99 (19) |
C6—C1—S1 | 119.31 (17) | C10—C11—C14 | 120.90 (19) |
C2—C1—S1 | 119.44 (17) | C13—C12—C11 | 122.0 (2) |
C3—C2—C1 | 118.5 (2) | C13—C12—H12 | 119.0 |
C3—C2—H2 | 120.7 | C11—C12—H12 | 119.0 |
C1—C2—H2 | 120.7 | C8—C13—C12 | 118.7 (2) |
C2—C3—C4 | 121.4 (2) | C8—C13—H13 | 120.7 |
C2—C3—H3 | 119.3 | C12—C13—H13 | 120.7 |
C4—C3—H3 | 119.3 | C15—C14—C19 | 116.86 (19) |
C5—C4—C3 | 118.7 (2) | C15—C14—C11 | 121.54 (19) |
C5—C4—C7 | 120.9 (2) | C19—C14—C11 | 121.6 (2) |
C3—C4—C7 | 120.5 (2) | C16—C15—C14 | 121.8 (2) |
C6—C5—C4 | 120.9 (2) | C16—C15—H15 | 119.1 |
C6—C5—H5 | 119.6 | C14—C15—H15 | 119.1 |
C4—C5—H5 | 119.6 | C17—C16—C15 | 120.5 (2) |
C5—C6—C1 | 119.3 (2) | C17—C16—H16 | 119.8 |
C5—C6—H6 | 120.4 | C15—C16—H16 | 119.8 |
C1—C6—H6 | 120.4 | C18—C17—C16 | 118.9 (2) |
C4—C7—H7A | 109.5 | C18—C17—H17 | 120.6 |
C4—C7—H7B | 109.5 | C16—C17—H17 | 120.6 |
H7A—C7—H7B | 109.5 | C17—C18—C19 | 120.7 (2) |
C4—C7—H7C | 109.5 | C17—C18—H18 | 119.7 |
H7A—C7—H7C | 109.5 | C19—C18—H18 | 119.7 |
H7B—C7—H7C | 109.5 | C18—C19—C14 | 121.4 (2) |
C13—C8—C9 | 121.8 (2) | C18—C19—H19 | 119.3 |
C13—C8—O3 | 118.8 (2) | C14—C19—H19 | 119.3 |
C9—C8—O3 | 119.2 (2) | ||
O2—S1—O3—C8 | 172.32 (15) | O3—C8—C9—C10 | −177.12 (19) |
O1—S1—O3—C8 | 43.04 (17) | C8—C9—C10—C11 | 0.3 (3) |
C1—S1—O3—C8 | −73.17 (17) | C9—C10—C11—C12 | 0.3 (3) |
O2—S1—C1—C6 | −143.74 (17) | C9—C10—C11—C14 | −179.9 (2) |
O1—S1—C1—C6 | −8.8 (2) | C10—C11—C12—C13 | −0.6 (3) |
O3—S1—C1—C6 | 106.90 (17) | C14—C11—C12—C13 | 179.5 (2) |
O2—S1—C1—C2 | 36.7 (2) | C9—C8—C13—C12 | 0.3 (3) |
O1—S1—C1—C2 | 171.61 (16) | O3—C8—C13—C12 | 176.82 (19) |
O3—S1—C1—C2 | −72.69 (17) | C11—C12—C13—C8 | 0.3 (3) |
C6—C1—C2—C3 | −1.1 (3) | C12—C11—C14—C15 | 179.7 (2) |
S1—C1—C2—C3 | 178.48 (15) | C10—C11—C14—C15 | −0.1 (3) |
C1—C2—C3—C4 | 0.3 (3) | C12—C11—C14—C19 | 0.0 (3) |
C2—C3—C4—C5 | 1.0 (3) | C10—C11—C14—C19 | −179.9 (2) |
C2—C3—C4—C7 | −179.0 (2) | C19—C14—C15—C16 | −0.4 (3) |
C3—C4—C5—C6 | −1.5 (3) | C11—C14—C15—C16 | 179.9 (2) |
C7—C4—C5—C6 | 178.5 (2) | C14—C15—C16—C17 | −0.1 (4) |
C4—C5—C6—C1 | 0.7 (3) | C15—C16—C17—C18 | 0.3 (4) |
C2—C1—C6—C5 | 0.6 (3) | C16—C17—C18—C19 | −0.1 (4) |
S1—C1—C6—C5 | −178.97 (16) | C17—C18—C19—C14 | −0.4 (4) |
S1—O3—C8—C13 | 101.5 (2) | C15—C14—C19—C18 | 0.7 (3) |
S1—O3—C8—C9 | −81.9 (2) | C11—C14—C19—C18 | −179.6 (2) |
C13—C8—C9—C10 | −0.6 (3) |
Funding information
Funding for this research was provided by: Narodowe Centrum Nauki (grant No. 2014/15/D/ST5/02731).
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