3,5-Di­meth­oxy­phenyl 4-methyl­benzene­sulfonate

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

doi:10.1107/S2414314617009804

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 7| July 2017| x170980

https://doi.org/10.1107/S2414314617009804

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3,5-Dimethoxyphenyl 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, 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 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 ). The dihedral angle between two aromatic moieties is 57.23 (4)°.

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

The crystal structure (Fig. 2) 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.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15A⋯O4ⁱ	0.96	2.35	3.2051 (18)	147
C15—H15C⋯O2ⁱⁱ	0.96	2.51	3.4063 (19)	155
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y+2, -z+1.

Figure 2
The crystal packing of the title compound, viewed along the c axis.

Synthesis 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 saturated solution was obtained. The solution was warmed, then left to stand in a 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	C₁₅H₁₆O₅S
M_r	308.34
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	7.8066 (2), 8.9238 (2), 11.9303 (3)
α, β, γ (°)	106.583 (2), 94.701 (2), 111.358 (2)
V (Å³)	725.58 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.24
Crystal size (mm)	0.26 × 0.25 × 0.24

Data collection
Diffractometer	Oxford Diffraction Xcalibur
No. of measured, independent and observed [I > 2σ(I)] reflections	4805, 2795, 2316
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.077, 1.05
No. of reflections	2795
No. of parameters	193
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.35
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: 1559861

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617009804/bt4054sup1.cif

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

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-Dimethoxyphenyl 4-methylbenzenesulfonate top

Crystal data top

C₁₅H₁₆O₅S	Z = 2
M_r = 308.34	F(000) = 324
Triclinic, P1	D_x = 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

Data collection top

Oxford Diffraction Xcalibur diffractometer	2316 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 = 3.1°
ω–scan	h = −8→9
4805 measured reflections	k = −10→10
2795 independent reflections	l = −14→14

Refinement top

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(F_o²) + (0.0437P)² + 0.0255P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2795 reflections	Δρ_max = 0.38 e Å⁻³
193 parameters	Δρ_min = −0.35 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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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).

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