organic compounds
3,5-Dimethoxyphenyl 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, C15H16O5S, are composed of a 3,5-dimethoxyphenyl moiety substituted with a toluene-4-sulfonate group. The dihedral angle between two aromatic rings is 57.23 (4)°. In the crystal, molecules are connected by weak C—H⋯O hydrogen bonds and S⋯O van der Waals interactions.
Keywords: crystal structure; tosylates; cross-coupling reactions.
CCDC reference: 1559861
Structure description
Aryl tosylates attract considerable attention as electrophiles in transition-metal-catalyzed cross-coupling reactions (Chen et al., 2015; Nguyen et al., 2003). 4-Methylbenzenesulfonate derivatives emerged as substrates for first-row transition metal catalysts. These non-precious transition metal elements are suitable alternatives to execute challenging cross-coupling with higher efficiency (Ananikov, 2015).
In the . In the molecular structure, the bond lengths and angles are within normal ranges (Allen et al., 2002). The dihedral angle between two aromatic moieties is 57.23 (4)°.
of the title compound there is one independent molecule. The molecular structure is shown in Fig. 1The ) features weak C—H⋯O hydrogen bonds (Table 1) and S1⋯O1i van der Waals interactions [symmetry code: (i) −x + 2, −y + 2, −z + 1. The S1⋯O1i distance is 3.2929 (10) Å]. The S1⋯O1i contacts connect the molecules into dimers, while C—H⋯O bonds arrange the molecules into chains along b axis.
(Fig. 2Synthesis and crystallization
3,5-Dimethoxyphenyl 4-methylbenzenesulfonate was synthesized according to the 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 a refrigerator (−20°C).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1559861
https://doi.org/10.1107/S2414314617009804/bt4054sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617009804/bt4054Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617009804/bt4054Isup3.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).C15H16O5S | Z = 2 |
Mr = 308.34 | F(000) = 324 |
Triclinic, P1 | Dx = 1.411 Mg m−3 |
a = 7.8066 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.9238 (2) Å | Cell parameters from 4805 reflections |
c = 11.9303 (3) Å | θ = 3.1–26.0° |
α = 106.583 (2)° | µ = 0.24 mm−1 |
β = 94.701 (2)° | T = 100 K |
γ = 111.358 (2)° | Irregular, colourless |
V = 725.58 (3) Å3 | 0.26 × 0.25 × 0.24 mm |
Oxford Diffraction Xcalibur diffractometer | 2316 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 = 3.1° |
ω–scan | h = −8→9 |
4805 measured reflections | k = −10→10 |
2795 independent reflections | l = −14→14 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.0437P)2 + 0.0255P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2795 reflections | Δρmax = 0.38 e Å−3 |
193 parameters | Δρmin = −0.35 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 | ||
S1 | 0.73013 (5) | 0.83595 (4) | 0.47367 (3) | 0.01539 (11) | |
O1 | 0.81146 (14) | 0.96873 (12) | 0.42577 (9) | 0.0195 (2) | |
C1 | 0.80548 (19) | 0.67126 (18) | 0.41824 (12) | 0.0147 (3) | |
C2 | 0.91926 (19) | 0.68105 (18) | 0.33471 (12) | 0.0157 (3) | |
H2 | 0.9673 | 0.7794 | 0.3145 | 0.019* | |
O2 | 0.73567 (14) | 0.87416 (13) | 0.59863 (9) | 0.0217 (2) | |
O3 | 0.50777 (13) | 0.74229 (12) | 0.41772 (8) | 0.0157 (2) | |
C3 | 0.95988 (19) | 0.54111 (18) | 0.28197 (12) | 0.0168 (3) | |
H3 | 1.0349 | 0.5460 | 0.2253 | 0.020* | |
C4 | 0.89064 (19) | 0.39332 (18) | 0.31217 (12) | 0.0166 (3) | |
O4 | 0.26779 (15) | 0.29839 (13) | 0.04463 (9) | 0.0234 (3) | |
C5 | 0.78274 (19) | 0.39000 (18) | 0.39973 (12) | 0.0173 (3) | |
H5 | 0.7394 | 0.2940 | 0.4229 | 0.021* | |
O5 | 0.32254 (15) | 0.85268 (13) | 0.06289 (9) | 0.0221 (2) | |
C6 | 0.7393 (2) | 0.52739 (18) | 0.45258 (12) | 0.0165 (3) | |
H6 | 0.6665 | 0.5236 | 0.5105 | 0.020* | |
C8 | 0.44594 (18) | 0.69113 (18) | 0.29240 (12) | 0.0148 (3) | |
C7 | 0.9329 (2) | 0.24146 (19) | 0.25186 (14) | 0.0224 (3) | |
H7A | 0.8954 | 0.2084 | 0.1667 | 0.034* | |
H7B | 0.8649 | 0.1479 | 0.2774 | 0.034* | |
H7C | 1.0653 | 0.2714 | 0.2730 | 0.034* | |
C9 | 0.39824 (19) | 0.52299 (18) | 0.22586 (12) | 0.0163 (3) | |
H9 | 0.4173 | 0.4479 | 0.2607 | 0.020* | |
C10 | 0.3204 (2) | 0.46833 (18) | 0.10448 (13) | 0.0173 (3) | |
C11 | 0.29768 (19) | 0.58182 (18) | 0.05261 (12) | 0.0172 (3) | |
H11 | 0.2472 | 0.5449 | −0.0287 | 0.021* | |
C12 | 0.3511 (2) | 0.75243 (19) | 0.12328 (13) | 0.0163 (3) | |
C13 | 0.42417 (19) | 0.80989 (18) | 0.24526 (12) | 0.0157 (3) | |
H13 | 0.4570 | 0.9227 | 0.2931 | 0.019* | |
C14 | 0.1783 (2) | 0.2341 (2) | −0.07898 (13) | 0.0261 (4) | |
H14A | 0.2629 | 0.2905 | −0.1225 | 0.039* | |
H14B | 0.0668 | 0.2557 | −0.0868 | 0.039* | |
H14C | 0.1451 | 0.1132 | −0.1106 | 0.039* | |
C15 | 0.3825 (2) | 1.0314 (2) | 0.12916 (14) | 0.0275 (4) | |
H15A | 0.3640 | 1.0896 | 0.0759 | 0.041* | |
H15B | 0.5134 | 1.0791 | 0.1661 | 0.041* | |
H15C | 0.3102 | 1.0449 | 0.1897 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.01689 (19) | 0.01626 (19) | 0.01268 (19) | 0.00745 (15) | 0.00219 (13) | 0.00373 (14) |
O1 | 0.0201 (5) | 0.0157 (5) | 0.0223 (6) | 0.0064 (4) | 0.0022 (4) | 0.0074 (4) |
C1 | 0.0143 (7) | 0.0157 (7) | 0.0124 (7) | 0.0067 (6) | −0.0007 (5) | 0.0026 (6) |
C2 | 0.0148 (7) | 0.0159 (7) | 0.0139 (7) | 0.0036 (6) | 0.0006 (6) | 0.0058 (6) |
O2 | 0.0265 (6) | 0.0261 (6) | 0.0124 (5) | 0.0139 (5) | 0.0019 (4) | 0.0024 (4) |
O3 | 0.0157 (5) | 0.0206 (5) | 0.0119 (5) | 0.0081 (4) | 0.0040 (4) | 0.0056 (4) |
C3 | 0.0144 (7) | 0.0214 (8) | 0.0142 (7) | 0.0069 (6) | 0.0037 (6) | 0.0057 (6) |
C4 | 0.0142 (7) | 0.0172 (7) | 0.0160 (7) | 0.0065 (6) | −0.0008 (6) | 0.0033 (6) |
O4 | 0.0343 (6) | 0.0172 (6) | 0.0176 (6) | 0.0134 (5) | 0.0002 (5) | 0.0020 (4) |
C5 | 0.0160 (7) | 0.0167 (7) | 0.0189 (7) | 0.0048 (6) | 0.0014 (6) | 0.0086 (6) |
O5 | 0.0329 (6) | 0.0195 (6) | 0.0188 (5) | 0.0137 (5) | 0.0041 (5) | 0.0097 (4) |
C6 | 0.0158 (7) | 0.0202 (8) | 0.0139 (7) | 0.0067 (6) | 0.0040 (6) | 0.0069 (6) |
C8 | 0.0120 (7) | 0.0207 (8) | 0.0121 (7) | 0.0067 (6) | 0.0036 (5) | 0.0056 (6) |
C7 | 0.0242 (8) | 0.0205 (8) | 0.0237 (8) | 0.0106 (7) | 0.0069 (7) | 0.0066 (7) |
C9 | 0.0166 (7) | 0.0190 (7) | 0.0185 (8) | 0.0102 (6) | 0.0049 (6) | 0.0097 (6) |
C10 | 0.0174 (7) | 0.0162 (7) | 0.0187 (8) | 0.0090 (6) | 0.0048 (6) | 0.0033 (6) |
C11 | 0.0176 (7) | 0.0213 (8) | 0.0129 (7) | 0.0089 (6) | 0.0027 (6) | 0.0047 (6) |
C12 | 0.0156 (7) | 0.0199 (8) | 0.0188 (7) | 0.0097 (6) | 0.0068 (6) | 0.0103 (6) |
C13 | 0.0150 (7) | 0.0147 (7) | 0.0180 (7) | 0.0068 (6) | 0.0060 (6) | 0.0047 (6) |
C14 | 0.0329 (9) | 0.0219 (8) | 0.0185 (8) | 0.0128 (7) | −0.0013 (7) | −0.0006 (7) |
C15 | 0.0440 (10) | 0.0207 (8) | 0.0242 (9) | 0.0174 (8) | 0.0080 (7) | 0.0112 (7) |
S1—O2 | 1.4244 (10) | C6—H6 | 0.9300 |
S1—O1 | 1.4254 (10) | C8—C9 | 1.373 (2) |
S1—O3 | 1.6101 (10) | C8—C13 | 1.3871 (19) |
S1—C1 | 1.7556 (14) | C7—H7A | 0.9600 |
S1—O1i | 3.2929 (10) | C7—H7B | 0.9600 |
C1—C2 | 1.3885 (19) | C7—H7C | 0.9600 |
C1—C6 | 1.3910 (19) | C9—C10 | 1.3931 (19) |
C2—C3 | 1.3887 (19) | C9—H9 | 0.9300 |
C2—H2 | 0.9300 | C10—C11 | 1.382 (2) |
O3—C8 | 1.4171 (15) | C11—C12 | 1.396 (2) |
C3—C4 | 1.395 (2) | C11—H11 | 0.9300 |
C3—H3 | 0.9300 | C12—C13 | 1.3896 (19) |
C4—C5 | 1.3947 (19) | C13—H13 | 0.9300 |
C4—C7 | 1.5070 (19) | C14—H14A | 0.9600 |
O4—C10 | 1.3633 (17) | C14—H14B | 0.9600 |
O4—C14 | 1.4313 (17) | C14—H14C | 0.9600 |
C5—C6 | 1.383 (2) | C15—H15A | 0.9600 |
C5—H5 | 0.9300 | C15—H15B | 0.9600 |
O5—C12 | 1.3623 (17) | C15—H15C | 0.9600 |
O5—C15 | 1.4366 (18) | ||
O2—S1—O1 | 120.88 (6) | C4—C7—H7A | 109.5 |
O2—S1—O3 | 102.37 (6) | C4—C7—H7B | 109.5 |
O1—S1—O3 | 108.43 (5) | H7A—C7—H7B | 109.5 |
O2—S1—C1 | 110.89 (6) | C4—C7—H7C | 109.5 |
O1—S1—C1 | 110.05 (6) | H7A—C7—H7C | 109.5 |
O3—S1—C1 | 102.28 (6) | H7B—C7—H7C | 109.5 |
O2—S1—O1i | 80.61 (5) | C8—C9—C10 | 117.91 (13) |
O1—S1—O1i | 68.92 (5) | C8—C9—H9 | 121.0 |
O3—S1—O1i | 176.85 (4) | C10—C9—H9 | 121.0 |
C1—S1—O1i | 77.41 (5) | O4—C10—C11 | 124.24 (13) |
C2—C1—C6 | 121.02 (13) | O4—C10—C9 | 115.06 (12) |
C2—C1—S1 | 119.61 (11) | C11—C10—C9 | 120.70 (13) |
C6—C1—S1 | 119.22 (11) | C10—C11—C12 | 119.46 (13) |
C1—C2—C3 | 118.68 (13) | C10—C11—H11 | 120.3 |
C1—C2—H2 | 120.7 | C12—C11—H11 | 120.3 |
C3—C2—H2 | 120.7 | O5—C12—C13 | 124.31 (13) |
C8—O3—S1 | 118.80 (8) | O5—C12—C11 | 114.44 (13) |
C2—C3—C4 | 121.42 (13) | C13—C12—C11 | 121.24 (13) |
C2—C3—H3 | 119.3 | C8—C13—C12 | 116.89 (13) |
C4—C3—H3 | 119.3 | C8—C13—H13 | 121.6 |
C5—C4—C3 | 118.48 (13) | C12—C13—H13 | 121.6 |
C5—C4—C7 | 120.97 (13) | O4—C14—H14A | 109.5 |
C3—C4—C7 | 120.55 (13) | O4—C14—H14B | 109.5 |
C10—O4—C14 | 117.21 (11) | H14A—C14—H14B | 109.5 |
C6—C5—C4 | 120.99 (13) | O4—C14—H14C | 109.5 |
C6—C5—H5 | 119.5 | H14A—C14—H14C | 109.5 |
C4—C5—H5 | 119.5 | H14B—C14—H14C | 109.5 |
C12—O5—C15 | 117.31 (12) | O5—C15—H15A | 109.5 |
C5—C6—C1 | 119.33 (13) | O5—C15—H15B | 109.5 |
C5—C6—H6 | 120.3 | H15A—C15—H15B | 109.5 |
C1—C6—H6 | 120.3 | O5—C15—H15C | 109.5 |
C9—C8—C13 | 123.77 (13) | H15A—C15—H15C | 109.5 |
C9—C8—O3 | 117.73 (12) | H15B—C15—H15C | 109.5 |
C13—C8—O3 | 118.33 (12) | ||
O2—S1—C1—C2 | −139.74 (11) | S1—C1—C6—C5 | 173.38 (11) |
O1—S1—C1—C2 | −3.35 (13) | S1—O3—C8—C9 | 98.87 (13) |
O3—S1—C1—C2 | 111.74 (11) | S1—O3—C8—C13 | −85.70 (13) |
O1i—S1—C1—C2 | −65.06 (11) | C13—C8—C9—C10 | −1.2 (2) |
O2—S1—C1—C6 | 44.73 (13) | O3—C8—C9—C10 | 173.96 (11) |
O1—S1—C1—C6 | −178.88 (11) | C14—O4—C10—C11 | −2.0 (2) |
O3—S1—C1—C6 | −63.80 (12) | C14—O4—C10—C9 | 176.90 (13) |
O1i—S1—C1—C6 | 119.40 (11) | C8—C9—C10—O4 | −176.98 (12) |
C6—C1—C2—C3 | 2.6 (2) | C8—C9—C10—C11 | 1.9 (2) |
S1—C1—C2—C3 | −172.83 (10) | O4—C10—C11—C12 | 177.91 (12) |
O2—S1—O3—C8 | 177.23 (9) | C9—C10—C11—C12 | −0.9 (2) |
O1—S1—O3—C8 | 48.40 (11) | C15—O5—C12—C13 | 3.8 (2) |
C1—S1—O3—C8 | −67.86 (10) | C15—O5—C12—C11 | −177.20 (12) |
C1—C2—C3—C4 | −0.7 (2) | C10—C11—C12—O5 | 179.96 (12) |
C2—C3—C4—C5 | −1.7 (2) | C10—C11—C12—C13 | −1.0 (2) |
C2—C3—C4—C7 | 178.63 (13) | C9—C8—C13—C12 | −0.6 (2) |
C3—C4—C5—C6 | 2.3 (2) | O3—C8—C13—C12 | −175.70 (11) |
C7—C4—C5—C6 | −178.07 (13) | O5—C12—C13—C8 | −179.37 (13) |
C4—C5—C6—C1 | −0.4 (2) | C11—C12—C13—C8 | 1.7 (2) |
C2—C1—C6—C5 | −2.1 (2) |
Symmetry code: (i) −x+2, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15A···O4ii | 0.96 | 2.35 | 3.2051 (18) | 147 |
C15—H15C···O2iii | 0.96 | 2.51 | 3.4063 (19) | 155 |
Symmetry codes: (ii) x, y+1, z; (iii) −x+1, −y+2, −z+1. |
Funding information
Funding for this research was provided by: Narodowe Centrum Nauki (grant No. 2014/15/D/ST5/02731).
References
Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Ananikov, V. P. (2015). ACS Catal. 5, 1964–1971. Web of Science CrossRef CAS Google Scholar
Chen, X., Quan, Z.-J. & Wang, X.-C. (2015). Appl. Organomet. Chem. 29, 296–300. Web of Science CrossRef CAS Google Scholar
Nguyen, H. N., Huang, X. & Buchwald, S. L. (2003). J. Am. Chem. Soc. 125, 11818–11819. Web of Science CrossRef PubMed CAS 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
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