organic compounds
4-Chloronaphthalen-1-yl 4-methylbenzenesulfonate
aFaculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland
*Correspondence e-mail: bzarychta@uni.opole.pl
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 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 . 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)°.
of the title compound. The molecular structure is shown in Fig. 1In 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.
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 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 .
details are summarized in Table 2Structural data
CCDC reference: 1849905
https://doi.org/10.1107/S2414314618008891/sj4183sup1.cif
contains datablocks I, global. DOI: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
Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell
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).C17H13ClO3S | F(000) = 688 |
Mr = 332.78 | Dx = 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 |
Oxford Diffraction Xcalibur diffractometer | 2515 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm-1 | θmax = 26.0°, θmin = 3.4° |
ω scan | h = −16→16 |
10121 measured reflections | k = −14→8 |
2950 independent reflections | l = −12→12 |
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(Fo2) + (0.0373P)2 + 0.4347P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2950 reflections | Δρmax = 0.40 e Å−3 |
200 parameters | Δρmin = −0.34 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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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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