Biphenyl-4-yl 4-methyl­benzene­sulfonate

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

doi:10.1107/S2414314617009828

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 7| July 2017| x170982

https://doi.org/10.1107/S2414314617009828

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Biphenyl-4-yl 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, 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 asymmetric unit of the title compound, there is one independent molecule. The crystal is twinned by inversion. 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 the two coplanar biphenyl rings and the toluene ring is 52.72 (6)°. The crystal packing is shown in Fig. 2.

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

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

Synthesis 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 saturated solution 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 refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₉H₁₆O₃S
M_r	324.38
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	100
a, b, c (Å)	33.2932 (10), 7.9284 (2), 5.7903 (2)
V (Å³)	1528.42 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.23
Crystal size (mm)	0.3 × 0.25 × 0.12

Data collection
Diffractometer	Oxford Diffraction Xcalibur
No. of measured, independent and observed [I > 2σ(I)] reflections	9829, 2222, 1978
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.057, 0.98
No. of reflections	2222
No. of parameters	210
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.27
Absolute structure	Refined as an inversion twin.
Absolute structure parameter	0.32 (11)
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: 1560198

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617009828/bt4056sup1.cif

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

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).

Biphenyl-4-yl 4-methylbenzenesulfonate top

Crystal data top

C₁₉H₁₆O₃S	D_x = 1.410 Mg m⁻³
M_r = 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

Data collection top

Oxford Diffraction Xcalibur diffractometer	1978 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.027
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	θ_max = 26.0°, θ_min = 3.2°
ω–scan	h = −41→40
9829 measured reflections	k = −9→9
2222 independent reflections	l = −4→7

Refinement top

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(F_o²) + (0.0347P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.057	(Δ/σ)_max < 0.001
S = 0.98	Δρ_max = 0.15 e Å⁻³
2222 reflections	Δρ_min = −0.27 e Å⁻³
210 parameters	Absolute structure: Refined as an inversion twin.
1 restraint	Absolute structure parameter: 0.32 (11)

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. 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 C_aromatic—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	0.32398 (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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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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