4-Chloro­naphthalen-1-yl 4-methyl­benzene­sulfonate

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

doi:10.1107/S2414314618008891

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 6| June 2018| x180889

https://doi.org/10.1107/S2414314618008891

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4-Chloronaphthalen-1-yl 4-methylbenzenesulfonate

Aleksandra Piontek,^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 J. Simpson, University of Otago, New Zealand (Received 12 June 2018; accepted 18 June 2018; online 22 June 2018)

In the title compound, C₁₇H₁₃ClO₃S, the naphthalene ring system and the benzene ring of the tosylate substituent are inclined to one another by 55.32 (5)°. The crystal structure features weak intermolecular C—H⋯O hydrogen bonds, one of which forms inversion dimers. Additional C—H⋯O hydrogen bonds and weak Cl⋯Cl halogen bonds stack the molecules along the b-axis direction.

Keywords: tosylates; crystal structure; cross-coupling reactions.

CCDC reference: 1849905

Structure description

Aryl tosylates are important intermediates in organic synthesis (Hugo et al., 2014 ; Xu & Zhang, 2011 ; Grandane et al., 2012 ). These compounds are easily prepared from cheap, readily available starting materials and are convenient to handle, stable crystalline solids (Bisz & Szostak, 2017a ,b ). These advantages make them ideal substrates in cross-coupling reactions (Piontek et al., 2017 ; Ackermann et al., 2006 ; Bisz et al., 2018 ).

There is one independent molecule in the asymmetric unit of the title compound. The molecular structure is shown in Fig. 1. The molecule consists of a naphthalene ring system substituted at C1 by a 4-methylbenzenesulfonate group and with a chlorine substituent at C4. The dihedral angle between the naphthalene ring system (r.m.s. deviation = 0.0104 Å) and the benzene ring is 55.32 (5)°.

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

In the crystal, C2—H2⋯O2 hydrogen bonds, Table 1, form inversion dimers that enclose R₂²(14) rings. Additional C12—H12⋯O3 and C16—H16⋯O1 hydrogen bonds link adjacent dimers, forming double rows of molecules along the bc diagonal, Fig. 2. Weak Cl1⋯Cl1(1 − x, 1 − y, −z) halogen bonds [3.6817 (8) Å] also occur. These contacts combine to stack the molecules along the b-axis direction, Fig. 3.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2ⁱ	0.93	2.53	3.2651 (19)	136
C12—H12⋯O3ⁱⁱ	0.93	2.53	3.3050 (18)	141
C16—H16⋯O1ⁱⁱⁱ	0.93	2.53	3.3192 (18)	143
Symmetry codes: (i) -x, -y+1, -z; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
Rows of molecules along the bc diagonal. Hydrogen bonds are shown as blue dashed lines.

Figure 3
Overall packing viewed along the b-axis direction. Representative Cl⋯Cl contacts are shown as green dotted lines.

Synthesis and crystallization

The compound was synthesized according to a previously described procedure (Murai et al., 2012 ). The crystallization was carried out in diethyl ether, previously stored over sodium. Diethyl ether (0.8 ml) was placed in a storage reaction vial (8 ml) provided with a silicone septum. The title compound was added to diethyl ether until a saturated solution was obtained. The solution was then heated to the boiling point of the solvent and the vial was screwed off with a silicone septum stopper. The resulting solution was then heated and left to stand in a refrigerator (−20°C), yielding colourless crystals suitable for data collection.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₃ClO₃S
M_r	332.78
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	13.1301 (3), 11.9592 (2), 10.3738 (3)
β (°)	112.041 (3)
V (Å³)	1509.90 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.40
Crystal size (mm)	0.5 × 0.45 × 0.4

Data collection
Diffractometer	Oxford Diffraction Xcalibur
No. of measured, independent and observed [I > 2σ(I)] reflections	10121, 2950, 2515
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.072, 1.06
No. of reflections	2950
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.34
Computer programs: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction, (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1849905

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314618008891/sj4183sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618008891/sj4183Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618008891/sj4183Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis CCD (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

4-Chloronaphthalen-1-yl 4-methylbenzenesulfonate top

Crystal data top

C₁₇H₁₃ClO₃S	F(000) = 688
M_r = 332.78	D_x = 1.464 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.1301 (3) Å	Cell parameters from 10121 reflections
b = 11.9592 (2) Å	θ = 3.4–26.0°
c = 10.3738 (3) Å	µ = 0.40 mm⁻¹
β = 112.041 (3)°	T = 100 K
V = 1509.90 (7) Å³	Irregular, colourless
Z = 4	0.5 × 0.45 × 0.4 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer	2515 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	θ_max = 26.0°, θ_min = 3.4°
ω scan	h = −16→16
10121 measured reflections	k = −14→8
2950 independent reflections	l = −12→12

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.026	H-atom parameters constrained
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0373P)² + 0.4347P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2950 reflections	Δρ_max = 0.40 e Å⁻³
200 parameters	Δρ_min = −0.34 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.03474 (3)	0.34571 (3)	0.29668 (4)	0.01694 (11)
Cl1	0.44738 (3)	0.56968 (3)	0.12070 (4)	0.02886 (12)
O1	0.13270 (8)	0.29057 (8)	0.26065 (11)	0.0190 (2)
O2	−0.04014 (9)	0.39892 (9)	0.17485 (11)	0.0238 (3)
O3	−0.00103 (9)	0.25441 (9)	0.35695 (11)	0.0234 (3)
C1	0.20522 (12)	0.36011 (12)	0.22530 (15)	0.0175 (3)
C2	0.16998 (13)	0.42354 (13)	0.10778 (15)	0.0213 (3)
H2	0.0963	0.4236	0.0490	0.026*
C3	0.24673 (13)	0.48882 (13)	0.07683 (15)	0.0226 (3)
H3	0.2236	0.5340	−0.0019	0.027*
C4	0.35509 (13)	0.48629 (13)	0.16182 (16)	0.0204 (3)
C5	0.50724 (12)	0.41223 (12)	0.37265 (16)	0.0199 (3)
H5	0.5592	0.4534	0.3518	0.024*
C6	0.53989 (13)	0.34678 (13)	0.48863 (17)	0.0227 (3)
H6	0.6138	0.3436	0.5461	0.027*
C7	0.46217 (13)	0.28373 (13)	0.52221 (17)	0.0232 (3)
H7	0.4852	0.2399	0.6021	0.028*
C8	0.35365 (13)	0.28673 (12)	0.43820 (16)	0.0199 (3)
H8	0.3033	0.2444	0.4608	0.024*
C9	0.31700 (12)	0.35393 (12)	0.31654 (15)	0.0162 (3)
C10	0.39536 (12)	0.41840 (12)	0.28356 (15)	0.0169 (3)
C11	0.10147 (11)	0.44694 (12)	0.42155 (14)	0.0144 (3)
C12	0.09851 (12)	0.55841 (12)	0.38264 (15)	0.0178 (3)
H12	0.0603	0.5802	0.2910	0.021*
C13	0.15371 (12)	0.63630 (12)	0.48313 (16)	0.0195 (3)
H13	0.1521	0.7112	0.4584	0.023*
C14	0.21162 (11)	0.60499 (13)	0.62050 (15)	0.0174 (3)
C15	0.21289 (12)	0.49281 (13)	0.65634 (15)	0.0202 (3)
H15	0.2511	0.4709	0.7479	0.024*
C16	0.15807 (13)	0.41343 (13)	0.55780 (15)	0.0196 (3)
H16	0.1592	0.3386	0.5826	0.023*
C17	0.26993 (13)	0.69201 (14)	0.72763 (17)	0.0246 (4)
H17A	0.3185	0.7342	0.6965	0.037*
H17B	0.3116	0.6560	0.8141	0.037*
H17C	0.2169	0.7413	0.7406	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01306 (18)	0.01679 (19)	0.0198 (2)	−0.00117 (14)	0.00481 (15)	−0.00584 (14)
Cl1	0.0303 (2)	0.0307 (2)	0.0308 (2)	0.00058 (17)	0.01738 (19)	0.00840 (17)
O1	0.0171 (5)	0.0170 (5)	0.0246 (6)	−0.0006 (4)	0.0096 (5)	−0.0057 (4)
O2	0.0168 (5)	0.0287 (6)	0.0202 (6)	0.0022 (5)	0.0003 (5)	−0.0063 (5)
O3	0.0215 (6)	0.0195 (6)	0.0312 (6)	−0.0065 (4)	0.0123 (5)	−0.0071 (5)
C1	0.0184 (7)	0.0157 (7)	0.0203 (8)	−0.0004 (6)	0.0093 (6)	−0.0057 (6)
C2	0.0192 (8)	0.0254 (8)	0.0166 (7)	0.0034 (6)	0.0037 (6)	−0.0050 (6)
C3	0.0273 (8)	0.0244 (8)	0.0159 (7)	0.0077 (7)	0.0079 (7)	0.0026 (6)
C4	0.0242 (8)	0.0200 (8)	0.0213 (8)	0.0022 (6)	0.0136 (7)	−0.0002 (6)
C5	0.0181 (7)	0.0181 (8)	0.0264 (8)	0.0017 (6)	0.0116 (7)	−0.0015 (6)
C6	0.0181 (8)	0.0228 (8)	0.0251 (8)	0.0056 (6)	0.0057 (7)	0.0002 (7)
C7	0.0240 (8)	0.0229 (8)	0.0226 (8)	0.0075 (7)	0.0087 (7)	0.0062 (7)
C8	0.0223 (8)	0.0174 (7)	0.0237 (8)	0.0028 (6)	0.0126 (7)	0.0010 (6)
C9	0.0178 (7)	0.0148 (7)	0.0175 (7)	0.0033 (6)	0.0084 (6)	−0.0031 (6)
C10	0.0192 (7)	0.0152 (7)	0.0181 (7)	0.0031 (6)	0.0090 (6)	−0.0025 (6)
C11	0.0126 (7)	0.0146 (7)	0.0163 (7)	−0.0010 (5)	0.0056 (6)	−0.0038 (6)
C12	0.0189 (7)	0.0181 (7)	0.0150 (7)	0.0033 (6)	0.0047 (6)	0.0013 (6)
C13	0.0218 (8)	0.0142 (7)	0.0230 (8)	−0.0003 (6)	0.0088 (7)	0.0002 (6)
C14	0.0123 (7)	0.0215 (8)	0.0205 (8)	−0.0026 (6)	0.0085 (6)	−0.0057 (6)
C15	0.0209 (8)	0.0248 (8)	0.0133 (7)	0.0008 (6)	0.0047 (6)	0.0013 (6)
C16	0.0243 (8)	0.0161 (7)	0.0190 (7)	−0.0001 (6)	0.0089 (7)	0.0023 (6)
C17	0.0193 (8)	0.0290 (9)	0.0248 (8)	−0.0070 (7)	0.0075 (7)	−0.0108 (7)

Geometric parameters (Å, º) top

S1—O3	1.4226 (11)	C7—H7	0.9300
S1—O2	1.4270 (11)	C8—C9	1.419 (2)
S1—O1	1.6093 (10)	C8—H8	0.9300
S1—C11	1.7491 (14)	C9—C10	1.426 (2)
Cl1—C4	1.7415 (16)	C11—C16	1.386 (2)
O1—C1	1.4124 (17)	C11—C12	1.389 (2)
C1—C2	1.361 (2)	C12—C13	1.383 (2)
C1—C9	1.419 (2)	C12—H12	0.9300
C2—C3	1.404 (2)	C13—C14	1.391 (2)
C2—H2	0.9300	C13—H13	0.9300
C3—C4	1.364 (2)	C14—C15	1.391 (2)
C3—H3	0.9300	C14—C17	1.505 (2)
C4—C10	1.426 (2)	C15—C16	1.383 (2)
C5—C6	1.363 (2)	C15—H15	0.9300
C5—C10	1.414 (2)	C16—H16	0.9300
C5—H5	0.9300	C17—H17A	0.9600
C6—C7	1.414 (2)	C17—H17B	0.9600
C6—H6	0.9300	C17—H17C	0.9600
C7—C8	1.363 (2)

O3—S1—O2	120.01 (7)	C1—C9—C8	122.92 (14)
O3—S1—O1	102.24 (6)	C1—C9—C10	118.07 (13)
O2—S1—O1	108.79 (6)	C8—C9—C10	119.01 (13)
O3—S1—C11	111.22 (7)	C5—C10—C4	123.91 (14)
O2—S1—C11	109.54 (7)	C5—C10—C9	118.76 (13)
O1—S1—C11	103.51 (6)	C4—C10—C9	117.33 (13)
C1—O1—S1	119.63 (9)	C16—C11—C12	121.29 (13)
C2—C1—O1	121.67 (13)	C16—C11—S1	118.87 (11)
C2—C1—C9	123.06 (14)	C12—C11—S1	119.83 (11)
O1—C1—C9	115.18 (13)	C13—C12—C11	118.54 (13)
C1—C2—C3	118.87 (14)	C13—C12—H12	120.7
C1—C2—H2	120.6	C11—C12—H12	120.7
C3—C2—H2	120.6	C12—C13—C14	121.41 (14)
C4—C3—C2	120.26 (14)	C12—C13—H13	119.3
C4—C3—H3	119.9	C14—C13—H13	119.3
C2—C3—H3	119.9	C15—C14—C13	118.72 (13)
C3—C4—C10	122.37 (14)	C15—C14—C17	121.19 (14)
C3—C4—Cl1	118.80 (12)	C13—C14—C17	120.08 (14)
C10—C4—Cl1	118.83 (12)	C16—C15—C14	120.93 (14)
C6—C5—C10	120.84 (14)	C16—C15—H15	119.5
C6—C5—H5	119.6	C14—C15—H15	119.5
C10—C5—H5	119.6	C15—C16—C11	119.10 (14)
C5—C6—C7	120.46 (14)	C15—C16—H16	120.4
C5—C6—H6	119.8	C11—C16—H16	120.4
C7—C6—H6	119.8	C14—C17—H17A	109.5
C8—C7—C6	120.43 (14)	C14—C17—H17B	109.5
C8—C7—H7	119.8	H17A—C17—H17B	109.5
C6—C7—H7	119.8	C14—C17—H17C	109.5
C7—C8—C9	120.50 (14)	H17A—C17—H17C	109.5
C7—C8—H8	119.8	H17B—C17—H17C	109.5
C9—C8—H8	119.8

O3—S1—O1—C1	−166.82 (10)	C3—C4—C10—C9	−1.6 (2)
O2—S1—O1—C1	65.27 (11)	Cl1—C4—C10—C9	178.03 (10)
C11—S1—O1—C1	−51.16 (11)	C1—C9—C10—C5	−179.34 (13)
S1—O1—C1—C2	−65.00 (16)	C8—C9—C10—C5	0.6 (2)
S1—O1—C1—C9	118.30 (12)	C1—C9—C10—C4	1.07 (19)
O1—C1—C2—C3	−178.46 (12)	C8—C9—C10—C4	−178.95 (13)
C9—C1—C2—C3	−2.0 (2)	O3—S1—C11—C16	30.20 (14)
C1—C2—C3—C4	1.5 (2)	O2—S1—C11—C16	165.20 (12)
C2—C3—C4—C10	0.3 (2)	O1—S1—C11—C16	−78.90 (13)
C2—C3—C4—Cl1	−179.32 (11)	O3—S1—C11—C12	−150.85 (12)
C10—C5—C6—C7	−0.1 (2)	O2—S1—C11—C12	−15.85 (14)
C5—C6—C7—C8	0.7 (2)	O1—S1—C11—C12	100.05 (12)
C6—C7—C8—C9	−0.6 (2)	C16—C11—C12—C13	0.1 (2)
C2—C1—C9—C8	−179.28 (13)	S1—C11—C12—C13	−178.83 (11)
O1—C1—C9—C8	−2.6 (2)	C11—C12—C13—C14	0.2 (2)
C2—C1—C9—C10	0.7 (2)	C12—C13—C14—C15	−0.4 (2)
O1—C1—C9—C10	177.35 (11)	C12—C13—C14—C17	−179.41 (14)
C7—C8—C9—C1	179.90 (14)	C13—C14—C15—C16	0.2 (2)
C7—C8—C9—C10	−0.1 (2)	C17—C14—C15—C16	179.22 (14)
C6—C5—C10—C4	179.00 (14)	C14—C15—C16—C11	0.1 (2)
C6—C5—C10—C9	−0.6 (2)	C12—C11—C16—C15	−0.3 (2)
C3—C4—C10—C5	178.87 (15)	S1—C11—C16—C15	178.66 (11)
Cl1—C4—C10—C5	−1.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱ	0.93	2.53	3.2651 (19)	136
C12—H12···O3ⁱⁱ	0.93	2.53	3.3050 (18)	141
C16—H16···O1ⁱⁱⁱ	0.93	2.53	3.3192 (18)	143

Symmetry codes: (i) −x, −y+1, −z; (ii) −x, y+1/2, −z+1/2; (iii) x, −y+1/2, z+1/2.

Funding information

We gratefully acknowledge Narodowe Centrum Nauki (grant No. 2014/15/D/ST5/02731).

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