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

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)°.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.036
• wR factor = 0.116
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    S1     --  O2      ..       7.80 su

Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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)°.

Related literature

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

S2. 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.

S3. Refinement

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

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).

Figures

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

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

Crystal data

C21H18O3S	F(000) = 736.00
Mr = 350.43	Dx = 1.310 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 11320 reflections
a = 19.8000 (7) Å	θ = 3.1–27.4°
b = 5.8289 (2) Å	µ = 0.20 mm^−1
c = 15.5228 (7) Å	T = 296 K
β = 97.2226 (12)°	Plate, colourless
V = 1777.31 (12) Å^3	0.50 × 0.50 × 0.20 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	2454 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.037
ω scans	θmax = 27.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −25→25
Tmin = 0.879, Tmax = 0.961	k = −6→7
16497 measured reflections	l = −20→20
4064 independent reflections

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.035	w = 1/[0.0007Fo^2 + σ(Fo^2)]/(4Fo^2)
wR(F^2) = 0.115	(Δ/σ)max < 0.001
S = 1.01	Δρmax = 0.32 e Å^−3
4064 reflections	Δρmin = −0.37 e Å^−3
245 parameters	Extinction correction: Larson (1970)
0 restraints	Extinction 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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.18392 (2)	0.36995 (9)	0.40582 (3)	0.04917 (14)
O1	0.24688 (6)	0.5425 (2)	0.41891 (8)	0.0490 (3)
O2	0.20815 (6)	0.1464 (2)	0.39044 (10)	0.0626 (4)
O3	0.14984 (6)	0.4139 (2)	0.47932 (9)	0.0692 (4)
C1	0.30475 (8)	0.5083 (2)	0.37345 (12)	0.0423 (4)
C2	0.36167 (9)	0.4467 (3)	0.42212 (12)	0.0504 (5)
C3	0.43026 (8)	0.4338 (3)	0.39505 (12)	0.0457 (5)
C4	0.47282 (10)	0.2516 (3)	0.42163 (13)	0.0588 (6)
C5	0.53825 (10)	0.2424 (3)	0.40017 (14)	0.0636 (6)
C6	0.56265 (9)	0.4158 (3)	0.35334 (13)	0.0564 (6)
C7	0.52180 (9)	0.5978 (3)	0.32689 (13)	0.0564 (6)
C8	0.45589 (9)	0.6074 (3)	0.34753 (12)	0.0528 (5)
C9	0.29281 (8)	0.5511 (2)	0.27937 (12)	0.0399 (4)
C10	0.31048 (9)	0.3861 (3)	0.22233 (12)	0.0463 (5)
C11	0.29633 (10)	0.4197 (3)	0.13398 (12)	0.0563 (6)
C12	0.26427 (10)	0.6160 (3)	0.10150 (12)	0.0570 (6)
C13	0.24713 (9)	0.7817 (3)	0.15732 (13)	0.0554 (6)
C14	0.26083 (8)	0.7515 (3)	0.24614 (12)	0.0469 (5)
C15	0.13442 (8)	0.4713 (3)	0.31215 (12)	0.0437 (5)
C16	0.13277 (9)	0.3540 (3)	0.23505 (12)	0.0490 (5)
C17	0.09787 (9)	0.4460 (3)	0.16026 (13)	0.0551 (5)
C18	0.06416 (9)	0.6543 (3)	0.16162 (13)	0.0558 (6)
C19	0.06504 (9)	0.7662 (3)	0.24064 (16)	0.0588 (6)
C20	0.09969 (9)	0.6786 (3)	0.31559 (13)	0.0538 (5)
C21	0.02903 (12)	0.7611 (4)	0.07986 (17)	0.0876 (9)
H2	0.3579	0.4074	0.4794	0.060*
H4	0.4570	0.1340	0.4543	0.071*
H5	0.5659	0.1178	0.4176	0.076*
H6	0.6070	0.4097	0.3395	0.068*
H7	0.5383	0.7155	0.2949	0.068*
H8	0.4284	0.7320	0.3293	0.063*
H10	0.3320	0.2521	0.2436	0.056*
H11	0.3086	0.3082	0.0960	0.068*
H12	0.2543	0.6363	0.0418	0.068*
H13	0.2261	0.9158	0.1353	0.066*
H14	0.2488	0.8644	0.2837	0.056*
H16	0.1550	0.2138	0.2332	0.059*
H17	0.0970	0.3668	0.1081	0.066*
H19	0.0416	0.9038	0.2429	0.071*
H20	0.1000	0.7564	0.3679	0.065*
H211	0.0549	0.7310	0.0327	0.105*
H212	0.0255	0.9238	0.0878	0.105*
H213	−0.0157	0.6967	0.0668	0.105*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0464 (2)	0.0604 (3)	0.0419 (3)	−0.0014 (2)	0.0103 (2)	0.0001 (2)
O1	0.0444 (6)	0.0644 (8)	0.0398 (7)	−0.0042 (5)	0.0116 (5)	−0.0115 (6)
O2	0.0705 (8)	0.0510 (8)	0.0651 (10)	0.0076 (6)	0.0040 (7)	0.0045 (7)
O3	0.0573 (7)	0.1060 (12)	0.0483 (9)	−0.0027 (7)	0.0228 (6)	0.0018 (8)
C1	0.0413 (8)	0.0491 (10)	0.0376 (10)	−0.0001 (7)	0.0088 (7)	−0.0053 (8)
C2	0.0480 (9)	0.0689 (12)	0.0343 (10)	−0.0031 (9)	0.0054 (8)	0.0055 (9)
C3	0.0437 (9)	0.0600 (11)	0.0325 (10)	−0.0006 (8)	0.0018 (7)	0.0033 (8)
C4	0.0571 (11)	0.0653 (13)	0.0539 (13)	0.0045 (10)	0.0070 (9)	0.0190 (10)
C5	0.0534 (11)	0.0721 (14)	0.0648 (14)	0.0137 (10)	0.0058 (10)	0.0122 (12)
C6	0.0426 (9)	0.0760 (14)	0.0501 (12)	−0.0005 (10)	0.0040 (8)	−0.0036 (11)
C7	0.0472 (9)	0.0674 (13)	0.0548 (13)	−0.0070 (9)	0.0073 (9)	0.0082 (10)
C8	0.0494 (10)	0.0567 (11)	0.0516 (12)	0.0012 (9)	0.0042 (8)	0.0091 (10)
C9	0.0379 (8)	0.0456 (9)	0.0362 (10)	−0.0007 (7)	0.0053 (7)	−0.0021 (8)
C10	0.0493 (9)	0.0477 (10)	0.0425 (11)	0.0045 (8)	0.0090 (8)	−0.0040 (9)
C11	0.0644 (11)	0.0656 (13)	0.0404 (12)	−0.0031 (10)	0.0130 (9)	−0.0133 (10)
C12	0.0605 (11)	0.0732 (14)	0.0367 (11)	−0.0102 (10)	0.0032 (9)	0.0061 (10)
C13	0.0543 (10)	0.0537 (12)	0.0568 (13)	−0.0014 (9)	0.0020 (9)	0.0139 (10)
C14	0.0489 (9)	0.0448 (10)	0.0475 (12)	−0.0012 (8)	0.0082 (8)	−0.0029 (9)
C15	0.0386 (8)	0.0485 (10)	0.0450 (11)	−0.0022 (7)	0.0093 (7)	−0.0020 (8)
C16	0.0466 (9)	0.0489 (10)	0.0516 (12)	−0.0001 (8)	0.0073 (8)	−0.0067 (9)
C17	0.0523 (10)	0.0654 (12)	0.0471 (12)	−0.0056 (10)	0.0044 (9)	−0.0079 (10)
C18	0.0415 (9)	0.0679 (13)	0.0576 (14)	−0.0036 (9)	0.0046 (9)	0.0085 (11)
C19	0.0461 (10)	0.0553 (12)	0.0763 (16)	0.0075 (9)	0.0124 (10)	0.0068 (11)
C20	0.0513 (10)	0.0544 (11)	0.0580 (13)	0.0020 (9)	0.0160 (9)	−0.0078 (10)
C21	0.0740 (14)	0.105 (2)	0.0801 (19)	0.0060 (14)	−0.0029 (13)	0.0261 (16)

Geometric parameters (Å, º)

S1—O1	1.5946 (12)	C17—C18	1.387 (2)
S1—O2	1.4189 (14)	C18—C19	1.387 (3)
S1—O3	1.4200 (15)	C18—C21	1.503 (3)
S1—C15	1.7508 (17)	C19—C20	1.373 (2)
O1—C1	1.433 (2)	C2—H2	0.930
C1—C2	1.325 (2)	C4—H4	0.930
C1—C9	1.471 (2)	C5—H5	0.930
C2—C3	1.473 (2)	C6—H6	0.930
C3—C4	1.386 (2)	C7—H7	0.930
C3—C8	1.386 (2)	C8—H8	0.930
C4—C5	1.379 (2)	C10—H10	0.930
C5—C6	1.368 (3)	C11—H11	0.930
C6—C7	1.366 (2)	C12—H12	0.930
C7—C8	1.383 (2)	C13—H13	0.930
C9—C10	1.382 (2)	C14—H14	0.930
C9—C14	1.396 (2)	C16—H16	0.930
C10—C11	1.379 (2)	C17—H17	0.930
C11—C12	1.374 (2)	C19—H19	0.930
C12—C13	1.368 (3)	C20—H20	0.930
C13—C14	1.383 (2)	C21—H211	0.960
C15—C16	1.375 (2)	C21—H212	0.960
C15—C20	1.395 (2)	C21—H213	0.960
C16—C17	1.382 (2)
O1—S1—O2	108.97 (7)	C1—C2—H2	116.6
O1—S1—O3	103.10 (8)	C3—C2—H2	116.6
O1—S1—C15	103.89 (7)	C3—C4—H4	119.6
O2—S1—O3	120.38 (9)	C5—C4—H4	119.6
O2—S1—C15	109.63 (8)	C4—C5—H5	119.8
O3—S1—C15	109.48 (8)	C6—C5—H5	119.8
S1—O1—C1	120.67 (10)	C5—C6—H6	120.1
O1—C1—C2	115.62 (16)	C7—C6—H6	120.1
O1—C1—C9	115.25 (13)	C6—C7—H7	119.9
C2—C1—C9	129.13 (17)	C8—C7—H7	119.9
C1—C2—C3	126.85 (18)	C3—C8—H8	119.6
C2—C3—C4	120.13 (17)	C7—C8—H8	119.6
C2—C3—C8	121.81 (16)	C9—C10—H10	119.9
C4—C3—C8	117.94 (16)	C11—C10—H10	119.9
C3—C4—C5	120.82 (19)	C10—C11—H11	119.7
C4—C5—C6	120.35 (19)	C12—C11—H11	119.7
C5—C6—C7	119.88 (18)	C11—C12—H12	120.1
C6—C7—C8	120.15 (19)	C13—C12—H12	120.1
C3—C8—C7	120.86 (17)	C12—C13—H13	119.7
C1—C9—C10	119.73 (15)	C14—C13—H13	119.7
C1—C9—C14	121.18 (16)	C9—C14—H14	120.1
C10—C9—C14	119.02 (17)	C13—C14—H14	120.1
C9—C10—C11	120.18 (17)	C15—C16—H16	120.2
C10—C11—C12	120.66 (19)	C17—C16—H16	120.2
C11—C12—C13	119.71 (18)	C16—C17—H17	119.4
C12—C13—C14	120.55 (18)	C18—C17—H17	119.4
C9—C14—C13	119.88 (17)	C18—C19—H19	119.2
S1—C15—C16	120.30 (13)	C20—C19—H19	119.2
S1—C15—C20	119.19 (14)	C15—C20—H20	120.5
C16—C15—C20	120.42 (16)	C19—C20—H20	120.5
C15—C16—C17	119.51 (17)	C18—C21—H211	109.5
C16—C17—C18	121.17 (19)	C18—C21—H212	109.5
C17—C18—C19	118.19 (18)	C18—C21—H213	109.5
C17—C18—C21	121.5 (2)	H211—C21—H212	109.5
C19—C18—C21	120.32 (19)	H211—C21—H213	109.5
C18—C19—C20	121.60 (18)	H212—C21—H213	109.5
C15—C20—C19	119.09 (19)
O2—S1—O1—C1	32.69 (14)	C3—C4—C5—C6	1.1 (3)
O3—S1—O1—C1	161.67 (12)	C4—C5—C6—C7	−0.7 (3)
O1—S1—C15—C16	106.36 (15)	C5—C6—C7—C8	0.1 (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—C11	176.68 (16)
O2—S1—C15—C16	−9.98 (17)	C1—C9—C14—C13	−176.66 (15)
O2—S1—C15—C20	173.46 (14)	C10—C9—C14—C13	0.2 (2)
O3—S1—C15—C16	−144.06 (15)	C14—C9—C10—C11	−0.3 (2)
O3—S1—C15—C20	39.38 (17)	C9—C10—C11—C12	−0.4 (2)
S1—O1—C1—C2	−110.89 (15)	C10—C11—C12—C13	1.0 (3)
S1—O1—C1—C9	70.28 (17)	C11—C12—C13—C14	−1.0 (2)
O1—C1—C2—C3	−170.22 (16)	C12—C13—C14—C9	0.4 (2)
O1—C1—C9—C10	−127.99 (16)	S1—C15—C16—C17	−174.80 (14)
O1—C1—C9—C14	48.9 (2)	S1—C15—C20—C19	175.21 (14)
C2—C1—C9—C10	53.4 (2)	C16—C15—C20—C19	−1.4 (2)
C2—C1—C9—C14	−129.8 (2)	C20—C15—C16—C17	1.7 (2)
C9—C1—C2—C3	8.4 (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—C8	45.6 (2)	C16—C17—C18—C21	176.93 (19)
C2—C3—C4—C5	−177.00 (18)	C17—C18—C19—C20	1.8 (2)
C2—C3—C8—C7	176.40 (18)	C21—C18—C19—C20	−176.57 (19)
C4—C3—C8—C7	0.4 (2)	C18—C19—C20—C15	−0.4 (2)
C8—C3—C4—C5	−1.0 (2)