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Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): o1787.
Published online 2008 August 20. doi:  10.1107/S160053680802607X
PMCID: PMC2960522

(E)-1,2-Diphenyl­vinyl p-toluene­sulfonate

Abstract

The title compound, C21H18O3S, is the E isomer, the ester ­oxy link being trans to one of the phenyl groups. The planes of the phenyl substituents at the vinyl C atoms form a dihedral angle of 66.32 (7)° with each other. The vinyl group shows noticeable non-planarity, the C(Ph)—C=C—C(Ph) torsion angle being 8.4 (3)°.

Related literature

For related literature, see: Ishikawa et al. (2001 [triangle]); Peterson & Indelicato (1968 [triangle]); Yoshihiro & Atsushi (1993 [triangle]); Larson (1970 [triangle]).

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Object name is e-64-o1787-scheme1.jpg

Experimental

Crystal data

  • C21H18O3S
  • M r = 350.43
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1787-efi1.jpg
  • a = 19.8000 (7) Å
  • b = 5.8289 (2) Å
  • c = 15.5228 (7) Å
  • β = 97.2226 (12)°
  • V = 1777.31 (12) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.20 mm−1
  • T = 296 (1) K
  • 0.50 × 0.50 × 0.20 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.879, T max = 0.961
  • 16497 measured reflections
  • 4064 independent reflections
  • 2454 reflections with I > 2σ(I)
  • R int = 0.037

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.115
  • S = 1.01
  • 4064 reflections
  • 245 parameters
  • H-atom parameters constrained
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.37 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 [triangle]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 [triangle]); program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680802607X/ya2077sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680802607X/ya2077Isup2.hkl

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

Acknowledgments

This work was partially supported by the Natural Science Foundation of China (20572094, 20672099). Mr Xinju Ma of the College of Pharmaceutical Science of Zhejiang University of Technology is acknowledged for interpretation and discussion of the structural results.

supplementary crystallographic information

Comment

The enol sulfonates have been extensively studied as substrates in solvolytic displacement reactions (Peterson & Indelicato, 1968) and as starting materials or intermediates in the synthesis of various medicines and agrichemicals (Yoshihiro & Atsushi, 1993). They also play important role in the synthesis of cephalosporin derivates (Ishikawa et al., 2001). As a part of our studies of enol sulfonates, we synthesized the title compound and determined its crystal structure.

The title compound is shown to be an E-isomer with the ester O1 oxygen in trans-position to the phenyl carbon atom C3. The C1=C2 double bond environment is notceably non-planar with the torsion angle C3—C2—C1—C9 being equal to 8.4 (3)°. The planes of Ph-groups C3—C8 and C9—C14 form dihedral angle of 66.32 (7)° with each other, whereas the C9—C14 plane is approximately parallel to the benzene plane C15—C20 of p-toluenesulfonic group; corresponding dihedral angle is equal to 10.5 (2)°.

Experimental

1,2-Diphenylethanone (0.84 mg, 4.3 mmol) in 2 ml of THF was slowly added to 5.00 mmol of freshly prepared lithium diisopropylamide at 195 K and stirred for 1 h. The resulting pale yellow solution was transferred to a solution of 3.0 g (9.2 mmol) of toluenesulfonic anhydride in 20 ml of THF at 273 K via a double-tip needle. This mixture was warmed to room temperature over a 3 h period and then poured into 200 ml of cold saturated NaHCO3. Extraction into ether (250 ml) was followed by washing with brine (250 ml) and water (250 ml) and drying (MgSO4). Evaporation of the solvent left a yellow-brown oil (0.94 g, 80% yield). Recrystallization from 20% ether/pentane gave colourless crystals.

Refinement

All H atoms were treated as riding atoms at distances of 0.93 (benzene), 0.96 (methyl) and 0.93 Å (methylene), with Uiso(H) = 1.2Ueq of the carrying atom.

Figures

Fig. 1.
Molecular structure of the title compound, showing 30% probability displacement ellipsoids and atom numbering scheme.

Crystal data

C21H18O3SF(000) = 736.00
Mr = 350.43Dx = 1.310 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybcCell parameters from 11320 reflections
a = 19.8000 (7) Åθ = 3.1–27.4°
b = 5.8289 (2) ŵ = 0.20 mm1
c = 15.5228 (7) ÅT = 296 K
β = 97.2226 (12)°Plate, colourless
V = 1777.31 (12) Å30.50 × 0.50 × 0.20 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer2454 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1Rint = 0.037
ω scansθmax = 27.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −25→25
Tmin = 0.879, Tmax = 0.961k = −6→7
16497 measured reflectionsl = −20→20
4064 independent reflections

Refinement

Refinement on F2H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.035w = 1/[0.0007Fo2 + σ(Fo2)]/(4Fo2)
wR(F2) = 0.115(Δ/σ)max < 0.001
S = 1.01Δρmax = 0.32 e Å3
4064 reflectionsΔρmin = −0.37 e Å3
245 parametersExtinction correction: Larson (1970)
0 restraintsExtinction coefficient: 704 (41)

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
S10.18392 (2)0.36995 (9)0.40582 (3)0.04917 (14)
O10.24688 (6)0.5425 (2)0.41891 (8)0.0490 (3)
O20.20815 (6)0.1464 (2)0.39044 (10)0.0626 (4)
O30.14984 (6)0.4139 (2)0.47932 (9)0.0692 (4)
C10.30475 (8)0.5083 (2)0.37345 (12)0.0423 (4)
C20.36167 (9)0.4467 (3)0.42212 (12)0.0504 (5)
C30.43026 (8)0.4338 (3)0.39505 (12)0.0457 (5)
C40.47282 (10)0.2516 (3)0.42163 (13)0.0588 (6)
C50.53825 (10)0.2424 (3)0.40017 (14)0.0636 (6)
C60.56265 (9)0.4158 (3)0.35334 (13)0.0564 (6)
C70.52180 (9)0.5978 (3)0.32689 (13)0.0564 (6)
C80.45589 (9)0.6074 (3)0.34753 (12)0.0528 (5)
C90.29281 (8)0.5511 (2)0.27937 (12)0.0399 (4)
C100.31048 (9)0.3861 (3)0.22233 (12)0.0463 (5)
C110.29633 (10)0.4197 (3)0.13398 (12)0.0563 (6)
C120.26427 (10)0.6160 (3)0.10150 (12)0.0570 (6)
C130.24713 (9)0.7817 (3)0.15732 (13)0.0554 (6)
C140.26083 (8)0.7515 (3)0.24614 (12)0.0469 (5)
C150.13442 (8)0.4713 (3)0.31215 (12)0.0437 (5)
C160.13277 (9)0.3540 (3)0.23505 (12)0.0490 (5)
C170.09787 (9)0.4460 (3)0.16026 (13)0.0551 (5)
C180.06416 (9)0.6543 (3)0.16162 (13)0.0558 (6)
C190.06504 (9)0.7662 (3)0.24064 (16)0.0588 (6)
C200.09969 (9)0.6786 (3)0.31559 (13)0.0538 (5)
C210.02903 (12)0.7611 (4)0.07986 (17)0.0876 (9)
H20.35790.40740.47940.060*
H40.45700.13400.45430.071*
H50.56590.11780.41760.076*
H60.60700.40970.33950.068*
H70.53830.71550.29490.068*
H80.42840.73200.32930.063*
H100.33200.25210.24360.056*
H110.30860.30820.09600.068*
H120.25430.63630.04180.068*
H130.22610.91580.13530.066*
H140.24880.86440.28370.056*
H160.15500.21380.23320.059*
H170.09700.36680.10810.066*
H190.04160.90380.24290.071*
H200.10000.75640.36790.065*
H2110.05490.73100.03270.105*
H2120.02550.92380.08780.105*
H213−0.01570.69670.06680.105*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0464 (2)0.0604 (3)0.0419 (3)−0.0014 (2)0.0103 (2)0.0001 (2)
O10.0444 (6)0.0644 (8)0.0398 (7)−0.0042 (5)0.0116 (5)−0.0115 (6)
O20.0705 (8)0.0510 (8)0.0651 (10)0.0076 (6)0.0040 (7)0.0045 (7)
O30.0573 (7)0.1060 (12)0.0483 (9)−0.0027 (7)0.0228 (6)0.0018 (8)
C10.0413 (8)0.0491 (10)0.0376 (10)−0.0001 (7)0.0088 (7)−0.0053 (8)
C20.0480 (9)0.0689 (12)0.0343 (10)−0.0031 (9)0.0054 (8)0.0055 (9)
C30.0437 (9)0.0600 (11)0.0325 (10)−0.0006 (8)0.0018 (7)0.0033 (8)
C40.0571 (11)0.0653 (13)0.0539 (13)0.0045 (10)0.0070 (9)0.0190 (10)
C50.0534 (11)0.0721 (14)0.0648 (14)0.0137 (10)0.0058 (10)0.0122 (12)
C60.0426 (9)0.0760 (14)0.0501 (12)−0.0005 (10)0.0040 (8)−0.0036 (11)
C70.0472 (9)0.0674 (13)0.0548 (13)−0.0070 (9)0.0073 (9)0.0082 (10)
C80.0494 (10)0.0567 (11)0.0516 (12)0.0012 (9)0.0042 (8)0.0091 (10)
C90.0379 (8)0.0456 (9)0.0362 (10)−0.0007 (7)0.0053 (7)−0.0021 (8)
C100.0493 (9)0.0477 (10)0.0425 (11)0.0045 (8)0.0090 (8)−0.0040 (9)
C110.0644 (11)0.0656 (13)0.0404 (12)−0.0031 (10)0.0130 (9)−0.0133 (10)
C120.0605 (11)0.0732 (14)0.0367 (11)−0.0102 (10)0.0032 (9)0.0061 (10)
C130.0543 (10)0.0537 (12)0.0568 (13)−0.0014 (9)0.0020 (9)0.0139 (10)
C140.0489 (9)0.0448 (10)0.0475 (12)−0.0012 (8)0.0082 (8)−0.0029 (9)
C150.0386 (8)0.0485 (10)0.0450 (11)−0.0022 (7)0.0093 (7)−0.0020 (8)
C160.0466 (9)0.0489 (10)0.0516 (12)−0.0001 (8)0.0073 (8)−0.0067 (9)
C170.0523 (10)0.0654 (12)0.0471 (12)−0.0056 (10)0.0044 (9)−0.0079 (10)
C180.0415 (9)0.0679 (13)0.0576 (14)−0.0036 (9)0.0046 (9)0.0085 (11)
C190.0461 (10)0.0553 (12)0.0763 (16)0.0075 (9)0.0124 (10)0.0068 (11)
C200.0513 (10)0.0544 (11)0.0580 (13)0.0020 (9)0.0160 (9)−0.0078 (10)
C210.0740 (14)0.105 (2)0.0801 (19)0.0060 (14)−0.0029 (13)0.0261 (16)

Geometric parameters (Å, °)

S1—O11.5946 (12)C17—C181.387 (2)
S1—O21.4189 (14)C18—C191.387 (3)
S1—O31.4200 (15)C18—C211.503 (3)
S1—C151.7508 (17)C19—C201.373 (2)
O1—C11.433 (2)C2—H20.930
C1—C21.325 (2)C4—H40.930
C1—C91.471 (2)C5—H50.930
C2—C31.473 (2)C6—H60.930
C3—C41.386 (2)C7—H70.930
C3—C81.386 (2)C8—H80.930
C4—C51.379 (2)C10—H100.930
C5—C61.368 (3)C11—H110.930
C6—C71.366 (2)C12—H120.930
C7—C81.383 (2)C13—H130.930
C9—C101.382 (2)C14—H140.930
C9—C141.396 (2)C16—H160.930
C10—C111.379 (2)C17—H170.930
C11—C121.374 (2)C19—H190.930
C12—C131.368 (3)C20—H200.930
C13—C141.383 (2)C21—H2110.960
C15—C161.375 (2)C21—H2120.960
C15—C201.395 (2)C21—H2130.960
C16—C171.382 (2)
O1—S1—O2108.97 (7)C1—C2—H2116.6
O1—S1—O3103.10 (8)C3—C2—H2116.6
O1—S1—C15103.89 (7)C3—C4—H4119.6
O2—S1—O3120.38 (9)C5—C4—H4119.6
O2—S1—C15109.63 (8)C4—C5—H5119.8
O3—S1—C15109.48 (8)C6—C5—H5119.8
S1—O1—C1120.67 (10)C5—C6—H6120.1
O1—C1—C2115.62 (16)C7—C6—H6120.1
O1—C1—C9115.25 (13)C6—C7—H7119.9
C2—C1—C9129.13 (17)C8—C7—H7119.9
C1—C2—C3126.85 (18)C3—C8—H8119.6
C2—C3—C4120.13 (17)C7—C8—H8119.6
C2—C3—C8121.81 (16)C9—C10—H10119.9
C4—C3—C8117.94 (16)C11—C10—H10119.9
C3—C4—C5120.82 (19)C10—C11—H11119.7
C4—C5—C6120.35 (19)C12—C11—H11119.7
C5—C6—C7119.88 (18)C11—C12—H12120.1
C6—C7—C8120.15 (19)C13—C12—H12120.1
C3—C8—C7120.86 (17)C12—C13—H13119.7
C1—C9—C10119.73 (15)C14—C13—H13119.7
C1—C9—C14121.18 (16)C9—C14—H14120.1
C10—C9—C14119.02 (17)C13—C14—H14120.1
C9—C10—C11120.18 (17)C15—C16—H16120.2
C10—C11—C12120.66 (19)C17—C16—H16120.2
C11—C12—C13119.71 (18)C16—C17—H17119.4
C12—C13—C14120.55 (18)C18—C17—H17119.4
C9—C14—C13119.88 (17)C18—C19—H19119.2
S1—C15—C16120.30 (13)C20—C19—H19119.2
S1—C15—C20119.19 (14)C15—C20—H20120.5
C16—C15—C20120.42 (16)C19—C20—H20120.5
C15—C16—C17119.51 (17)C18—C21—H211109.5
C16—C17—C18121.17 (19)C18—C21—H212109.5
C17—C18—C19118.19 (18)C18—C21—H213109.5
C17—C18—C21121.5 (2)H211—C21—H212109.5
C19—C18—C21120.32 (19)H211—C21—H213109.5
C18—C19—C20121.60 (18)H212—C21—H213109.5
C15—C20—C19119.09 (19)
O2—S1—O1—C132.69 (14)C3—C4—C5—C61.1 (3)
O3—S1—O1—C1161.67 (12)C4—C5—C6—C7−0.7 (3)
O1—S1—C15—C16106.36 (15)C5—C6—C7—C80.1 (2)
O1—S1—C15—C20−70.21 (15)C6—C7—C8—C3−0.0 (2)
C15—S1—O1—C1−84.11 (13)C1—C9—C10—C11176.68 (16)
O2—S1—C15—C16−9.98 (17)C1—C9—C14—C13−176.66 (15)
O2—S1—C15—C20173.46 (14)C10—C9—C14—C130.2 (2)
O3—S1—C15—C16−144.06 (15)C14—C9—C10—C11−0.3 (2)
O3—S1—C15—C2039.38 (17)C9—C10—C11—C12−0.4 (2)
S1—O1—C1—C2−110.89 (15)C10—C11—C12—C131.0 (3)
S1—O1—C1—C970.28 (17)C11—C12—C13—C14−1.0 (2)
O1—C1—C2—C3−170.22 (16)C12—C13—C14—C90.4 (2)
O1—C1—C9—C10−127.99 (16)S1—C15—C16—C17−174.80 (14)
O1—C1—C9—C1448.9 (2)S1—C15—C20—C19175.21 (14)
C2—C1—C9—C1053.4 (2)C16—C15—C20—C19−1.4 (2)
C2—C1—C9—C14−129.8 (2)C20—C15—C16—C171.7 (2)
C9—C1—C2—C38.4 (3)C15—C16—C17—C18−0.3 (2)
C1—C2—C3—C4−138.5 (2)C16—C17—C18—C19−1.4 (2)
C1—C2—C3—C845.6 (2)C16—C17—C18—C21176.93 (19)
C2—C3—C4—C5−177.00 (18)C17—C18—C19—C201.8 (2)
C2—C3—C8—C7176.40 (18)C21—C18—C19—C20−176.57 (19)
C4—C3—C8—C70.4 (2)C18—C19—C20—C15−0.4 (2)
C8—C3—C4—C5−1.0 (2)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: YA2077).

References

  • Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst.32, 115–119.
  • Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst.36, 1487.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Ishikawa, T., Kamiyama, K., Nakayama, Y., Iizawa, Y., Okonogi, K. & Miyake, A. (2001). J. Antibiot.54, 257–277. [PubMed]
  • Larson, A. C. (1970). Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, pp. 291–294. Copenhagen: Munksgaard.
  • Peterson, P. E. & Indelicato, J. M. (1968). J. Am. Chem. Soc.90, 6515–6516.
  • Rigaku (1998). PROCESS-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2004). CrystalStructure Rigaku/MSC, The Woodlands, Texas, USA.
  • Yoshihiro, U. & Atsushi, G. (1993). Jpn Patent No. 06-345 719.

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