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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o2011.
Published online 2009 July 29. doi:  10.1107/S1600536809029201
PMCID: PMC2977414

4-(4-Cyano-2-fluoro­phen­oxy)phenyl 4-methyl­benzene­sulfonate

Abstract

The title compound, C20H14FNO4S, was synthesized from hydro­quinone, p-toluene­sulfonyl chloride and 3,4-difluoro­benzonitrile. A folded conformation is adopted by the crystal structure. Inter­molecular C—H(...)N hydrogen bonds form dimers arranged around inversion centers.

Related literature

For the herbicidal activity of hydro­quinone derivatives, see: Bao et al. (2007 [triangle]); Liu (2002 [triangle]). For related structures, see: Chen & Zhang (2009 [triangle]); Han et al. (2008 [triangle]); Yang et al. (2008 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]); Etter (1990 [triangle]).

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Object name is e-65-o2011-scheme1.jpg

Experimental

Crystal data

  • C20H14FNO4S
  • M r = 383.39
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2011-efi1.jpg
  • a = 7.5504 (4) Å
  • b = 9.9558 (6) Å
  • c = 12.5862 (6) Å
  • α = 89.5250 (15)°
  • β = 77.8080 (12)°
  • γ = 81.9370 (15)°
  • V = 915.40 (9) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.21 mm−1
  • T = 296 K
  • 0.42 × 0.32 × 0.28 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.910, T max = 0.942
  • 9012 measured reflections
  • 4114 independent reflections
  • 2386 reflections with F 2 > 2σ(F 2)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.123
  • S = 1.01
  • 4114 reflections
  • 245 parameters
  • H-atom parameters constrained
  • Δρmax = 0.46 e Å−3
  • Δρmin = −0.50 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 [triangle]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 [triangle]), and Larson (1970 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: CrystalStructure.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029201/dn2473sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029201/dn2473Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The herbicidal activity of hydroquinone derivatives is well known in the art (Liu, 2002. Bao et al., 2007). As part of our ongoing studies, we now describe the synthesis and the crystal structure of the title compound.

As shown in Fig.1, the terminal C1—C7/S1 phenyl ring, the central benzene ring (C8—C13/O3/O4) and the other terminal phenyl ring (C14—C20/N1) form three planes, with max deviations for fitted atoms of 0.042 Å, 0.022Å and 0.013 Å, respectively. These planes make dihedral angles of 45.0 (1)° and 64.6 (6)° respectively. Otherwise, the molecule is bent at the sulfonate group with the C1—S1—O3—C8 torsion angle of 50.7 (3). The other bond parameters are similar to those observed in 4-Methyl-2-oxo-2,3-dihydro-1-benzopyran-7-yl benzenesulfonate (Yang et al., 2008), (E)-4-[(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl) iminomethyl]phenyl 4-bromobenzenesulfonate (Han et al., 2008) and 2-Methyl-3-nitrobenzyl cyanide (Chen et al., 2009).

In the crystal structure, the molecules are linked to form pseudo dimers by inter molecular C—H···N hydrogen bonds generating a graph set motif R22(10) (Table 1, Fig.2) (Etter, 1990, Bernstein et al., 1995). In addition, the structure is stabilized by weak C—H···O and van der Waal's interactions.

Experimental

A DMSO (10 ml) solution of hydroquinone and p-toluenesulfonyl chloride in the presence of KOH as base was stirred at room temperature for 48 h. Then the mixture was heated to 70°C and 3,4-difluorobenzonitrile was added dropwise. Finally the mixture was washed with water (20 ml) and extracted with ethyl acetate (three times). The organic solvent was removed under reduced pressure and the product was purified by silica gel chromatography (pentane: ethyl acetate mixtures). Suitable crystals were obtained by slow evaporation of ethanol at room temperature.

Refinement

All H atoms were placed in calculated positions with C—H = 0.93–0.98 Å, and were included in the refinement in the riding model with Uiso(H) = 1.2Ueq of the carrier atoms.

Figures

Fig. 1.
Molecular structure of title compound, with the atomic labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
A partial packing diagram of title compound. Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) -x+2, -y, -z+2].

Crystal data

C20H14FNO4SZ = 2
Mr = 383.39F(000) = 396.00
Triclinic, P1Dx = 1.391 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71075 Å
a = 7.5504 (4) ÅCell parameters from 5883 reflections
b = 9.9558 (6) Åθ = 3.2–27.4°
c = 12.5862 (6) ŵ = 0.21 mm1
α = 89.5250 (15)°T = 296 K
β = 77.8080 (12)°Chunk, colorless
γ = 81.9370 (15)°0.42 × 0.32 × 0.28 mm
V = 915.40 (9) Å3

Data collection

Rigaku R-AXIS RAPID diffractometer2386 reflections with F2 > 2σ(F2)
Detector resolution: 10.00 pixels mm-1Rint = 0.025
ω scansθmax = 27.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −9→9
Tmin = 0.910, Tmax = 0.942k = −12→12
9012 measured reflectionsl = −16→16
4114 independent reflections

Refinement

Refinement on F2w = 1/[0.0006Fo2 + 2σ(Fo2)]/(4Fo2)
R[F2 > 2σ(F2)] = 0.041(Δ/σ)max < 0.001
wR(F2) = 0.123Δρmax = 0.46 e Å3
S = 1.01Δρmin = −0.50 e Å3
4114 reflectionsExtinction correction: Larson (1970)
245 parametersExtinction coefficient: 591 (29)
H-atom parameters constrained

Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY
Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

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

xyzUiso*/Ueq
S10.16109 (6)0.69907 (6)0.48722 (4)0.05510 (18)
F10.3393 (2)0.2172 (2)1.07043 (12)0.1276 (7)
O10.0493 (2)0.78677 (14)0.43051 (12)0.0702 (5)
O20.2714 (2)0.58197 (13)0.43277 (12)0.0653 (4)
O30.01598 (18)0.65207 (16)0.58710 (12)0.0606 (4)
O40.2671 (2)0.4109 (2)0.93536 (12)0.0767 (6)
N11.1212 (3)0.0868 (3)0.8909 (2)0.1196 (11)
C10.2945 (2)0.7893 (2)0.54964 (16)0.0488 (6)
C20.4542 (2)0.7240 (2)0.57449 (19)0.0607 (7)
C30.5538 (2)0.7947 (2)0.6284 (2)0.0670 (8)
C40.4972 (3)0.9299 (2)0.65809 (18)0.0635 (7)
C50.3378 (3)0.9927 (2)0.63241 (19)0.0680 (7)
C60.2358 (3)0.9238 (2)0.57855 (18)0.0604 (7)
C70.6053 (4)1.0073 (3)0.7184 (2)0.0936 (10)
C80.0820 (2)0.5862 (2)0.67430 (18)0.0522 (6)
C90.1745 (2)0.4561 (2)0.66080 (18)0.0554 (6)
C100.2391 (2)0.3966 (2)0.74779 (18)0.0613 (7)
C110.2089 (2)0.4676 (2)0.84456 (18)0.0614 (7)
C120.1107 (3)0.5944 (2)0.8574 (2)0.0739 (8)
C130.0470 (3)0.6553 (2)0.7708 (2)0.0704 (8)
C140.4443 (3)0.3479 (2)0.92161 (17)0.0645 (7)
C150.4799 (3)0.2471 (3)0.99270 (19)0.0762 (8)
C160.6506 (3)0.1772 (2)0.98788 (19)0.0780 (8)
C170.7936 (3)0.2105 (2)0.90833 (18)0.0687 (8)
C180.7627 (3)0.3131 (2)0.8374 (2)0.0742 (8)
C190.5882 (3)0.3820 (2)0.84441 (19)0.0716 (8)
C200.9752 (3)0.1401 (3)0.8989 (2)0.0856 (10)
H20.49400.63320.55500.073*
H30.66110.75070.64520.080*
H50.29801.08360.65180.082*
H60.12830.96770.56190.072*
H90.19320.40930.59490.066*
H100.30260.30900.74070.074*
H120.08670.63990.92430.089*
H13−0.01880.74210.77860.085*
H160.67030.10901.03680.094*
H180.85940.33600.78470.089*
H190.56810.45160.79680.086*
H710.56300.99860.79530.112*
H720.58891.10140.70010.112*
H730.73280.97110.69810.112*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0528 (3)0.0515 (3)0.0600 (3)0.0018 (2)−0.0156 (2)0.0017 (2)
F10.0771 (10)0.191 (2)0.0934 (11)0.0040 (11)0.0113 (9)0.0689 (12)
O10.0738 (10)0.0636 (11)0.0790 (10)0.0040 (8)−0.0384 (9)0.0084 (8)
O20.0729 (10)0.0498 (10)0.0666 (9)0.0062 (8)−0.0093 (8)−0.0106 (7)
O30.0409 (7)0.0681 (10)0.0715 (9)−0.0008 (7)−0.0141 (7)0.0079 (8)
O40.0641 (10)0.1006 (16)0.0548 (9)0.0083 (10)−0.0018 (7)0.0114 (9)
N10.0747 (17)0.165 (2)0.1032 (19)0.0130 (18)−0.0039 (14)0.0380 (19)
C10.0450 (11)0.0443 (13)0.0541 (11)0.0034 (9)−0.0102 (9)0.0015 (9)
C20.0450 (12)0.0501 (14)0.0829 (15)0.0025 (11)−0.0104 (11)−0.0006 (12)
C30.0465 (12)0.0709 (18)0.0860 (17)−0.0043 (12)−0.0224 (12)0.0092 (14)
C40.0649 (15)0.0703 (18)0.0600 (13)−0.0209 (13)−0.0165 (11)0.0107 (12)
C50.0849 (17)0.0489 (15)0.0714 (15)−0.0026 (13)−0.0239 (13)−0.0035 (12)
C60.0632 (14)0.0500 (15)0.0671 (14)0.0072 (12)−0.0217 (11)−0.0003 (11)
C70.104 (2)0.102 (2)0.0925 (19)−0.0405 (19)−0.0434 (17)0.0119 (17)
C80.0375 (10)0.0554 (14)0.0617 (13)−0.0048 (10)−0.0070 (9)0.0044 (11)
C90.0535 (12)0.0537 (14)0.0606 (13)−0.0104 (11)−0.0140 (10)−0.0015 (11)
C100.0568 (13)0.0537 (15)0.0693 (15)−0.0022 (11)−0.0078 (11)0.0036 (12)
C110.0494 (13)0.0771 (18)0.0532 (13)−0.0028 (12)−0.0047 (10)0.0063 (12)
C120.0739 (16)0.082 (2)0.0560 (14)0.0051 (15)−0.0019 (12)−0.0138 (13)
C130.0649 (15)0.0649 (17)0.0692 (15)0.0126 (13)−0.0006 (12)−0.0062 (13)
C140.0558 (14)0.0872 (19)0.0487 (12)−0.0056 (13)−0.0100 (11)0.0058 (12)
C150.0596 (15)0.109 (2)0.0517 (13)−0.0074 (15)0.0026 (12)0.0185 (14)
C160.0692 (16)0.100 (2)0.0597 (14)−0.0042 (15)−0.0077 (13)0.0218 (14)
C170.0581 (14)0.091 (2)0.0558 (13)−0.0062 (13)−0.0126 (11)0.0020 (13)
C180.0587 (15)0.106 (2)0.0598 (14)−0.0209 (14)−0.0108 (11)0.0124 (14)
C190.0630 (15)0.092 (2)0.0617 (14)−0.0169 (14)−0.0156 (12)0.0184 (13)
C200.0653 (17)0.119 (2)0.0667 (16)0.0003 (17)−0.0093 (14)0.0178 (16)

Geometric parameters (Å, °)

S1—O11.4220 (16)C14—C151.376 (3)
S1—O21.4221 (13)C14—C191.375 (3)
S1—O31.5975 (14)C15—C161.366 (3)
S1—C11.744 (2)C16—C171.384 (3)
F1—C151.348 (2)C17—C181.379 (3)
O3—C81.418 (2)C17—C201.431 (3)
O4—C111.397 (2)C18—C191.383 (3)
O4—C141.371 (2)C2—H20.930
N1—C201.139 (3)C3—H30.930
C1—C21.382 (2)C5—H50.930
C1—C61.377 (3)C6—H60.930
C2—C31.375 (3)C7—H710.960
C3—C41.384 (3)C7—H720.960
C4—C51.376 (3)C7—H730.960
C4—C71.511 (4)C9—H90.930
C5—C61.378 (3)C10—H100.930
C8—C91.376 (3)C12—H120.930
C8—C131.359 (3)C13—H130.930
C9—C101.386 (3)C16—H160.930
C10—C111.374 (3)C18—H180.930
C11—C121.363 (3)C19—H190.930
C12—C131.384 (3)
O1—S1—O2119.42 (9)C16—C17—C18120.1 (2)
O1—S1—O3102.89 (8)C16—C17—C20120.8 (2)
O1—S1—C1111.32 (10)C18—C17—C20119.1 (2)
O2—S1—O3108.85 (8)C17—C18—C19120.2 (2)
O2—S1—C1109.48 (9)C14—C19—C18120.2 (2)
O3—S1—C1103.47 (8)N1—C20—C17178.4 (3)
S1—O3—C8118.35 (12)C1—C2—H2120.3
C11—O4—C14118.07 (15)C3—C2—H2120.3
S1—C1—C2119.91 (17)C2—C3—H3119.4
S1—C1—C6119.74 (16)C4—C3—H3119.4
C2—C1—C6120.3 (2)C4—C5—H5119.3
C1—C2—C3119.4 (2)C6—C5—H5119.3
C2—C3—C4121.2 (2)C1—C6—H6120.3
C3—C4—C5118.3 (2)C5—C6—H6120.3
C3—C4—C7121.3 (2)C4—C7—H71109.5
C5—C4—C7120.4 (2)C4—C7—H72109.5
C4—C5—C6121.4 (2)C4—C7—H73109.5
C1—C6—C5119.4 (2)H71—C7—H72109.5
O3—C8—C9120.46 (19)H71—C7—H73109.5
O3—C8—C13117.51 (19)H72—C7—H73109.5
C9—C8—C13122.0 (2)C8—C9—H9120.8
C8—C9—C10118.4 (2)C10—C9—H9120.8
C9—C10—C11119.7 (2)C9—C10—H10120.1
O4—C11—C10121.9 (2)C11—C10—H10120.1
O4—C11—C12117.2 (2)C11—C12—H12120.1
C10—C11—C12120.8 (2)C13—C12—H12120.1
C11—C12—C13119.9 (2)C8—C13—H13120.5
C8—C13—C12119.0 (2)C12—C13—H13120.5
O4—C14—C15117.19 (19)C15—C16—H16120.9
O4—C14—C19124.5 (2)C17—C16—H16120.9
C15—C14—C19118.3 (2)C17—C18—H18119.9
F1—C15—C14118.0 (2)C19—C18—H18119.9
F1—C15—C16119.1 (2)C14—C19—H19119.9
C14—C15—C16122.9 (2)C18—C19—H19119.9
C15—C16—C17118.3 (2)
O1—S1—O3—C8−166.73 (15)C4—C5—C6—C1−0.1 (2)
O1—S1—C1—C2−156.85 (16)O3—C8—C9—C10178.99 (19)
O1—S1—C1—C626.20 (19)O3—C8—C13—C12−179.5 (2)
O2—S1—O3—C865.64 (17)C9—C8—C13—C121.9 (3)
O2—S1—C1—C2−22.63 (19)C13—C8—C9—C10−2.4 (3)
O2—S1—C1—C6160.42 (16)C8—C9—C10—C110.3 (3)
O3—S1—C1—C293.29 (17)C9—C10—C11—O4178.3 (2)
O3—S1—C1—C6−83.66 (17)C9—C10—C11—C122.2 (3)
C1—S1—O3—C8−50.73 (17)O4—C11—C12—C13−179.1 (2)
S1—O3—C8—C9−71.2 (2)C10—C11—C12—C13−2.8 (3)
S1—O3—C8—C13110.10 (19)C11—C12—C13—C80.8 (3)
C11—O4—C14—C15−153.2 (2)O4—C14—C15—F10.0 (3)
C11—O4—C14—C1929.1 (3)O4—C14—C15—C16−179.7 (2)
C14—O4—C11—C1048.8 (3)O4—C14—C19—C18179.5 (2)
C14—O4—C11—C12−134.9 (2)C15—C14—C19—C181.8 (4)
S1—C1—C2—C3−176.91 (16)C19—C14—C15—F1177.9 (2)
S1—C1—C6—C5176.99 (16)C19—C14—C15—C16−1.9 (4)
C2—C1—C6—C50.1 (2)F1—C15—C16—C17−179.2 (2)
C6—C1—C2—C30.0 (2)C14—C15—C16—C170.5 (4)
C1—C2—C3—C4−0.1 (2)C15—C16—C17—C180.9 (4)
C2—C3—C4—C50.0 (2)C15—C16—C17—C20−179.6 (2)
C2—C3—C4—C7179.3 (2)C16—C17—C18—C19−0.9 (4)
C3—C4—C5—C60.0 (2)C20—C17—C18—C19179.6 (2)
C7—C4—C5—C6−179.3 (2)C17—C18—C19—C14−0.5 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C16—H16···N1i0.932.613.461 (3)152

Symmetry codes: (i) −x+2, −y, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2473).

References

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