Naphthalene-2,6-diyl bis­(4-methyl­benzene­sulfonate)

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

doi:10.1107/S2414314618008908

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 6| June 2018| x180890

https://doi.org/10.1107/S2414314618008908

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Naphthalene-2,6-diyl bis(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 W. T. A. Harrison, University of Aberdeen, Scotland (Received 12 June 2018; accepted 18 June 2018; online 22 June 2018)

The complete molecule of the title compound, C₂₄H₂₀O₆S₂, is generated by a crystallographic inversion centre at the middle of the naphthalene ring system. The dihedral angle between the naphthalene ring system and the pendant benzene ring is 10.23 (6)° and the C—S—O—C torsion angle is −172.05 (10)°. In the crystal, weak C—H⋯O interactions link the molecules into (10 $[\overline{1}]$ ) sheets.

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

CCDC reference: 1849908

Structure description

Aryl tosylates have attracted considerable attention as electrophiles in transition-metal catalyzed cross-coupling reactions (Piontek & Szostak, 2017 ; Chen et al., 2015 ; Ackermann et al., 2006 ). The use of these compounds can have advantages over the corresponding aryl halides in that the phenol group is a useful directing group for the introduction of other functional groups on the aromatic ring and as such can allow access to a wider substrate scope (Bisz & Szostak, 2017a ,b , 2018 ; Ackermann et al., 2006).

The asymmetric unit of the title compound consists of one independent half-molecule. The complete molecule is generated by an inversion centre at the middle of the C4—C4(2 − x, 1 − y, 1 − z) bond. The molecular structure is shown in Fig. 1.

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are generated by the symmetry operation 2 − x, 1 − y, 1 − z.

In the crystal, C—H⋯O hydrogen bonds (Table 1) connect the molecules into (10 $[\overline{1}]$ ) sheets (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.93	2.46	3.3261 (18)	156
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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

Synthesis and crystallization

The title compound was synthesized according to the procedure described by Murai et al. (2012 ). Diethyl ether (0.8 ml) was placed in a reaction vial (8 ml) provided with a rubber septum. The title compound was added to the diethyl ether until a saturated solution was obtained. The resulting solution was then heated and left to stand in a refrigerator (−20°C) and colourless irregular crystals formed.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₂₄H₂₀O₆S₂
M_r	468.52
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	12.2270 (3), 5.7229 (1), 15.9353 (5)
β (°)	109.869 (3)
V (Å³)	1048.68 (5)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.30
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	6789, 2046, 1806
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.082, 1.08
No. of reflections	2046
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.34
Computer programs: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b b) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1849908

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314618008908/hb4242sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618008908/hb4242Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618008908/hb4242Isup3.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: SHELXT2014 (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).

Naphthalene-2,6-diyl bis(4-methylbenzenesulfonate) top

Crystal data top

C₂₄H₂₀O₆S₂	F(000) = 488
M_r = 468.52	D_x = 1.484 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.2270 (3) Å	Cell parameters from 6789 reflections
b = 5.7229 (1) Å	θ = 3.5–26.0°
c = 15.9353 (5) Å	µ = 0.30 mm⁻¹
β = 109.869 (3)°	T = 100 K
V = 1048.68 (5) Å³	Irregular, colourless
Z = 2	0.5 × 0.45 × 0.4 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer	1806 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.016
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	θ_max = 26.0°, θ_min = 3.5°
ω scan	h = −15→15
6789 measured reflections	k = −6→7
2046 independent reflections	l = −19→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.0472P)² + 0.3531P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2046 reflections	Δρ_max = 0.37 e Å⁻³
146 parameters	Δρ_min = −0.34 e Å⁻³
0 restraints

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—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for C—H and with C—H₃ = 0.96 Å and U_iso = 1.5U_eq(C).

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

	x	y	z	U_iso*/U_eq
S1	0.60178 (3)	0.69746 (7)	0.34689 (2)	0.01589 (13)
O1	0.69632 (9)	0.56049 (19)	0.31607 (7)	0.0179 (3)
O2	0.61916 (9)	0.9428 (2)	0.34060 (7)	0.0237 (3)
O3	0.60474 (9)	0.6029 (2)	0.43036 (7)	0.0226 (3)
C1	0.81150 (12)	0.5696 (3)	0.37842 (9)	0.0152 (3)
C2	0.88107 (13)	0.7606 (3)	0.37395 (10)	0.0180 (3)
H2	0.8523	0.8769	0.3314	0.022*
C3	0.99199 (13)	0.7727 (3)	0.43334 (10)	0.0171 (3)
H3	1.0392	0.8981	0.4308	0.021*
C4	0.96386 (12)	0.4036 (3)	0.50119 (9)	0.0137 (3)
C5	0.84882 (13)	0.3929 (3)	0.43857 (10)	0.0157 (3)
H5	0.8002	0.2680	0.4387	0.019*
C6	0.47502 (12)	0.6087 (3)	0.26206 (10)	0.0145 (3)
C7	0.42327 (13)	0.7571 (3)	0.19026 (10)	0.0156 (3)
H7	0.4582	0.8978	0.1848	0.019*
C8	0.31833 (13)	0.6905 (3)	0.12701 (10)	0.0162 (3)
H8	0.2827	0.7883	0.0788	0.019*
C9	0.26556 (12)	0.4792 (3)	0.13462 (10)	0.0159 (3)
C10	0.32065 (13)	0.3337 (3)	0.20673 (10)	0.0170 (3)
H10	0.2866	0.1916	0.2119	0.020*
C11	0.42491 (13)	0.3965 (3)	0.27083 (10)	0.0173 (3)
H11	0.4608	0.2984	0.3189	0.021*
C12	0.15007 (14)	0.4100 (3)	0.06714 (11)	0.0222 (4)
H12A	0.0889	0.4959	0.0782	0.033*
H12B	0.1378	0.2456	0.0721	0.033*
H12C	0.1500	0.4445	0.0082	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0119 (2)	0.0182 (2)	0.0144 (2)	0.00249 (14)	0.00038 (15)	−0.00300 (14)
O1	0.0111 (5)	0.0247 (6)	0.0138 (5)	0.0040 (4)	−0.0010 (4)	−0.0040 (4)
O2	0.0192 (6)	0.0180 (6)	0.0273 (6)	0.0006 (5)	−0.0008 (5)	−0.0049 (5)
O3	0.0187 (6)	0.0327 (7)	0.0141 (5)	0.0033 (5)	0.0024 (4)	−0.0015 (5)
C1	0.0104 (7)	0.0217 (8)	0.0115 (7)	0.0021 (6)	0.0011 (6)	−0.0036 (6)
C2	0.0187 (8)	0.0200 (8)	0.0148 (7)	0.0046 (6)	0.0051 (6)	0.0052 (6)
C3	0.0164 (7)	0.0168 (8)	0.0190 (8)	−0.0009 (6)	0.0072 (6)	0.0028 (6)
C4	0.0135 (7)	0.0141 (7)	0.0140 (7)	0.0012 (6)	0.0054 (6)	−0.0014 (6)
C5	0.0131 (7)	0.0160 (8)	0.0179 (8)	−0.0006 (6)	0.0051 (6)	−0.0027 (6)
C6	0.0102 (7)	0.0169 (8)	0.0145 (7)	0.0017 (6)	0.0016 (6)	−0.0013 (6)
C7	0.0152 (7)	0.0146 (7)	0.0167 (8)	0.0010 (6)	0.0049 (6)	0.0003 (6)
C8	0.0151 (7)	0.0178 (8)	0.0142 (7)	0.0037 (6)	0.0031 (6)	0.0025 (6)
C9	0.0126 (7)	0.0198 (8)	0.0160 (7)	0.0009 (6)	0.0058 (6)	−0.0031 (6)
C10	0.0171 (8)	0.0142 (8)	0.0205 (8)	−0.0014 (6)	0.0073 (6)	−0.0004 (6)
C11	0.0171 (8)	0.0166 (8)	0.0168 (7)	0.0042 (6)	0.0038 (6)	0.0031 (6)
C12	0.0164 (8)	0.0271 (9)	0.0210 (8)	−0.0036 (7)	0.0036 (6)	−0.0012 (7)

Geometric parameters (Å, º) top

S1—O3	1.4249 (12)	C6—C11	1.389 (2)
S1—O2	1.4285 (12)	C6—C7	1.392 (2)
S1—O1	1.6056 (11)	C7—C8	1.389 (2)
S1—C6	1.7503 (15)	C7—H7	0.9300
O1—C1	1.4220 (17)	C8—C9	1.395 (2)
C1—C5	1.361 (2)	C8—H8	0.9300
C1—C2	1.401 (2)	C9—C10	1.393 (2)
C2—C3	1.366 (2)	C9—C12	1.508 (2)
C2—H2	0.9300	C10—C11	1.383 (2)
C3—C4ⁱ	1.419 (2)	C10—H10	0.9300
C3—H3	0.9300	C11—H11	0.9300
C4—C3ⁱ	1.419 (2)	C12—H12A	0.9600
C4—C4ⁱ	1.422 (3)	C12—H12B	0.9600
C4—C5	1.423 (2)	C12—H12C	0.9600
C5—H5	0.9300

O3—S1—O2	118.79 (7)	C11—C6—S1	118.77 (11)
O3—S1—O1	107.92 (6)	C7—C6—S1	119.57 (12)
O2—S1—O1	108.58 (7)	C8—C7—C6	118.61 (14)
O3—S1—C6	110.22 (7)	C8—C7—H7	120.7
O2—S1—C6	110.17 (7)	C6—C7—H7	120.7
O1—S1—C6	99.36 (6)	C7—C8—C9	121.02 (14)
C1—O1—S1	114.41 (9)	C7—C8—H8	119.5
C5—C1—C2	123.45 (14)	C9—C8—H8	119.5
C5—C1—O1	118.69 (13)	C10—C9—C8	118.78 (13)
C2—C1—O1	117.86 (13)	C10—C9—C12	120.27 (14)
C3—C2—C1	118.76 (14)	C8—C9—C12	120.94 (14)
C3—C2—H2	120.6	C11—C10—C9	121.33 (14)
C1—C2—H2	120.6	C11—C10—H10	119.3
C2—C3—C4ⁱ	120.85 (14)	C9—C10—H10	119.3
C2—C3—H3	119.6	C10—C11—C6	118.70 (14)
C4ⁱ—C3—H3	119.6	C10—C11—H11	120.6
C3ⁱ—C4—C4ⁱ	119.12 (16)	C6—C11—H11	120.6
C3ⁱ—C4—C5	121.55 (14)	C9—C12—H12A	109.5
C4ⁱ—C4—C5	119.33 (17)	C9—C12—H12B	109.5
C1—C5—C4	118.48 (14)	H12A—C12—H12B	109.5
C1—C5—H5	120.8	C9—C12—H12C	109.5
C4—C5—H5	120.8	H12A—C12—H12C	109.5
C11—C6—C7	121.55 (14)	H12B—C12—H12C	109.5

O3—S1—O1—C1	−57.12 (12)	O1—S1—C6—C11	84.27 (13)
O2—S1—O1—C1	72.86 (11)	O3—S1—C6—C7	147.51 (12)
C6—S1—O1—C1	−172.05 (10)	O2—S1—C6—C7	14.51 (14)
S1—O1—C1—C5	93.80 (14)	O1—S1—C6—C7	−99.35 (13)
S1—O1—C1—C2	−86.75 (14)	C11—C6—C7—C8	0.8 (2)
C5—C1—C2—C3	−0.6 (2)	S1—C6—C7—C8	−175.44 (11)
O1—C1—C2—C3	179.94 (13)	C6—C7—C8—C9	−0.2 (2)
C1—C2—C3—C4ⁱ	−0.4 (2)	C7—C8—C9—C10	−0.6 (2)
C2—C1—C5—C4	1.0 (2)	C7—C8—C9—C12	178.42 (14)
O1—C1—C5—C4	−179.60 (12)	C8—C9—C10—C11	0.9 (2)
C3ⁱ—C4—C5—C1	179.05 (14)	C12—C9—C10—C11	−178.12 (14)
C4ⁱ—C4—C5—C1	−0.3 (2)	C9—C10—C11—C6	−0.3 (2)
O3—S1—C6—C11	−28.87 (14)	C7—C6—C11—C10	−0.6 (2)
O2—S1—C6—C11	−161.87 (12)	S1—C6—C11—C10	175.75 (11)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱⁱ	0.93	2.46	3.3261 (18)	156

Symmetry code: (ii) −x+3/2, 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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