(2E,4E)-Ethyl 5-(phenyl­sulfon­yl)penta-2,4-dienoate

Sankar, U.; Sabari, V.; Suresh, G.; Uma, R.; Aravindhan, S.

doi:10.1107/S1600536812009907

organic compounds

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Volume 68| Part 4| April 2012| Page o1093

doi:10.1107/S1600536812009907

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(2E,4E)-Ethyl 5-(phenylsulfonyl)penta-2,4-dienoate

Ulaganathan Sankar,^a V. Sabari,^b G. Suresh,^b Ramakrishnan Uma ^a and S. Aravindhan ^b ^*

^aDepartment of Chemistry, Pachaiyappa's College, Chennai 600 030, India, and ^bDepartment of Physics, Presidency College, Chennai 600 005, India
^*Correspondence e-mail: arvindhanpresidency@gmail.com

(Received 23 February 2012; accepted 6 March 2012; online 17 March 2012)

In the title compound, C₁₃H₁₄O₄S, both C=C double bonds adopt an E conformation. In the crystal, molecules are linked into centrosymmetric R₂²(14) dimers via pairs of C—H⋯O hydrogen bonds.

Related literature

For the biological activity of phenyl sulfonyl-containing compounds see: De-Benedetti et al. (1985 ). For a related structure, see: Li (2011 ).

Experimental

Crystal data

C₁₃H₁₄O₄S
M_r = 266.30
Triclinic, $[P \overline 1]$
a = 6.2525 (3) Å
b = 7.8889 (4) Å
c = 14.5049 (7) Å
α = 82.828 (3)°
β = 87.261 (2)°
γ = 72.426 (2)°
V = 676.69 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 298 K
0.45 × 0.38 × 0.15 mm

Data collection

Bruker APEXII KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.899, T_max = 0.965
8948 measured reflections
3084 independent reflections
2621 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.147
S = 1.87
3084 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O3ⁱ	0.93	2.32	3.212 (2)	161
Symmetry code: (i) -x+2, -y, -z+1.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812009907/bt5831sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812009907/bt5831Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812009907/bt5831Isup3.cml

checkCIF report

Comment top

Phenyl sulfonyl containing compounds show a wide range of biological properties (De-Benedetti et al., 1985).

Fig. 1. shows a displacement ellipsoid plot of the title compound. Both C=C double bonds display an E configuration. The title molecule exhibits structural similarities with the already reported related structure (Li, 2011). The dihedral angle between two planes (C5—C6—S1—O1) and (C1—C6—S1—O2) is 37.32 (6)°. The crystal packing is stabilized by C—H···O intermolecular interactions. The molecules are linked into centrosymmetric R₂²(14) dimers via C7—H7···O3 hydrogen bonds (Table 1). The packing of the compound is shown in (Fig. 2).

Related literature top

For the biological activity of phenyl sulfonyl-containing compounds see: De-Benedetti et al. (1985). For a related structure, see: Li (2011).

Experimental top

LIHMDS (8 ml, 8.4 mmol, 1.06 molar solution in THF) was added drop wise to a 0 °C cooled solution of bisphenyl sulfonyl methane (1 g, 3.4 mmol) in dried THF (15 ml) under argon atmosphere. The reaction mixture was stirred at same temp for 1 h, and then trans ethyl 4-bromo coronate (0.71 g, 3.7 mmol) in dry THF (5 ml) was added dropwise and the reaction mixture was allowed to come to RT and it was stirred under argon atmosphere for 16 h. The reaction mixture was quenched by adding saturated NH₄Cl (20 ml) and then extracted with ethyl acetate (2x20 ml) and washed with water (2x20 ml) and sat brine (20 ml). Then, the organic layer was dried over MgSO₄. Evaporation of the solvent under vacuum furnished the crude product, the residue was chromatographed (25% ethyl acetate in hexanes) to give analytically pure (2E, 4E)-ethyl 5-(phenyl sulfonyl)penta-2,4-dienote (0.673 g. yield 75%) as a colorless solid.

Structure description top

Phenyl sulfonyl containing compounds show a wide range of biological properties (De-Benedetti et al., 1985).

For the biological activity of phenyl sulfonyl-containing compounds see: De-Benedetti et al. (1985). For a related structure, see: Li (2011).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are shown at 30% probability level. The H atoms are presented as a small spheres of arbitrary radius. Related atoms have symmetry code: (i) -x + 2, -y, -z + 1.
	Fig. 2. A view of the crystal packing. H atoms not involved in hydrogen bonding(dashed lines)have been omitted for clarity.

(2E,4E)-Ethyl 5-(phenylsulfonyl)penta-2,4-dienoate top

Crystal data top

C₁₃H₁₄O₄S	Z = 2
M_r = 266.30	F(000) = 280
Triclinic, P1	D_x = 1.307 Mg m⁻³
a = 6.2525 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.8889 (4) Å	Cell parameters from 5946 reflections
c = 14.5049 (7) Å	θ = 2.7–28.3°
α = 82.828 (3)°	µ = 0.24 mm⁻¹
β = 87.261 (2)°	T = 298 K
γ = 72.426 (2)°	Triclinic, colourless
V = 676.69 (6) Å³	0.45 × 0.38 × 0.15 mm

Data collection top

Bruker APEXII KappaCCD diffractometer	3084 independent reflections
Radiation source: fine-focus sealed tube	2621 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 15.9948 pixels mm^-1	θ_max = 28.4°, θ_min = 2.7°
ω and φ scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −10→9
T_min = 0.899, T_max = 0.965	l = −19→19
8948 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.147	w = 1/[σ²(F_o²) + (0.0551P)²] where P = (F_o² + 2F_c²)/3
S = 1.87	(Δ/σ)_max = 0.001
3084 reflections	Δρ_max = 0.29 e Å⁻³
164 parameters	Δρ_min = −0.30 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0173 (18)

Crystal data top

C₁₃H₁₄O₄S	γ = 72.426 (2)°
M_r = 266.30	V = 676.69 (6) Å³
Triclinic, P1	Z = 2
a = 6.2525 (3) Å	Mo Kα radiation
b = 7.8889 (4) Å	µ = 0.24 mm⁻¹
c = 14.5049 (7) Å	T = 298 K
α = 82.828 (3)°	0.45 × 0.38 × 0.15 mm
β = 87.261 (2)°

Data collection top

Bruker APEXII KappaCCD diffractometer	3084 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2621 reflections with I > 2σ(I)
T_min = 0.899, T_max = 0.965	R_int = 0.020
8948 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.147	H-atom parameters constrained
S = 1.87	Δρ_max = 0.29 e Å⁻³
3084 reflections	Δρ_min = −0.30 e Å⁻³
164 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
C1	1.5671 (3)	−0.0639 (2)	0.13787 (12)	0.0577 (4)
H1	1.6549	−0.0001	0.1586	0.069*
C2	1.6638 (3)	−0.2359 (3)	0.11608 (12)	0.0670 (5)
H2	1.8179	−0.2881	0.1219	0.080*
C3	1.5361 (3)	−0.3300 (2)	0.08618 (12)	0.0634 (5)
H3	1.6035	−0.4465	0.0726	0.076*
C4	1.3103 (3)	−0.2555 (3)	0.07586 (14)	0.0714 (5)
H4	1.2246	−0.3206	0.0549	0.086*
C5	1.2088 (3)	−0.0820 (2)	0.09680 (12)	0.0612 (4)
H5	1.0550	−0.0299	0.0895	0.073*
C6	1.3387 (2)	0.0124 (2)	0.12854 (9)	0.0446 (3)
C7	1.0978 (3)	0.1812 (2)	0.27041 (10)	0.0534 (4)
H7	1.1952	0.1132	0.3169	0.064*
C8	0.8815 (3)	0.2378 (2)	0.29034 (11)	0.0545 (4)
H8	0.7812	0.3023	0.2441	0.065*
C9	0.7980 (3)	0.2008 (2)	0.38347 (11)	0.0585 (4)
H9	0.9013	0.1296	0.4271	0.070*
C10	0.5861 (3)	0.2604 (2)	0.41125 (11)	0.0603 (4)
H10	0.4768	0.3307	0.3697	0.072*
C11	0.5253 (3)	0.2140 (3)	0.50916 (12)	0.0616 (4)
C12	0.2457 (4)	0.2713 (3)	0.62613 (15)	0.0902 (7)
H12A	0.2830	0.1440	0.6466	0.108*
H12B	0.3229	0.3242	0.6655	0.108*
C13	0.0051 (4)	0.3538 (4)	0.63268 (17)	0.1022 (8)
H13A	−0.0313	0.4779	0.6084	0.153*
H13B	−0.0420	0.3436	0.6966	0.153*
H13C	−0.0704	0.2944	0.5974	0.153*
O1	1.0292 (2)	0.32081 (16)	0.09966 (8)	0.0719 (4)
O2	1.3810 (2)	0.30846 (17)	0.17469 (9)	0.0749 (4)
O3	0.6500 (2)	0.1095 (2)	0.56403 (9)	0.0889 (5)
O4	0.3154 (2)	0.3006 (2)	0.52876 (8)	0.0778 (4)
S1	1.20983 (6)	0.22766 (5)	0.16117 (3)	0.05254 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0426 (8)	0.0583 (10)	0.0721 (10)	−0.0123 (7)	0.0000 (7)	−0.0144 (8)
C2	0.0466 (9)	0.0661 (12)	0.0762 (11)	0.0015 (8)	0.0056 (8)	−0.0106 (9)
C3	0.0706 (11)	0.0474 (9)	0.0635 (9)	−0.0046 (8)	0.0109 (8)	−0.0111 (7)
C4	0.0729 (12)	0.0618 (12)	0.0873 (12)	−0.0260 (10)	0.0008 (10)	−0.0236 (10)
C5	0.0462 (8)	0.0578 (10)	0.0782 (11)	−0.0109 (8)	−0.0021 (8)	−0.0140 (8)
C6	0.0428 (7)	0.0419 (8)	0.0454 (7)	−0.0087 (6)	0.0009 (6)	−0.0020 (6)
C7	0.0576 (9)	0.0475 (9)	0.0494 (8)	−0.0075 (7)	−0.0029 (7)	−0.0041 (6)
C8	0.0565 (9)	0.0496 (9)	0.0516 (8)	−0.0064 (7)	−0.0025 (7)	−0.0074 (7)
C9	0.0590 (10)	0.0562 (10)	0.0548 (9)	−0.0099 (8)	−0.0007 (7)	−0.0047 (7)
C10	0.0572 (10)	0.0603 (11)	0.0552 (9)	−0.0060 (8)	−0.0003 (7)	−0.0046 (8)
C11	0.0595 (10)	0.0586 (11)	0.0615 (10)	−0.0110 (8)	0.0010 (8)	−0.0047 (8)
C12	0.0948 (15)	0.0925 (16)	0.0674 (11)	−0.0119 (13)	0.0204 (11)	0.0019 (11)
C13	0.0908 (16)	0.122 (2)	0.0886 (15)	−0.0233 (15)	0.0273 (13)	−0.0240 (15)
O1	0.0726 (8)	0.0597 (8)	0.0600 (7)	0.0108 (6)	−0.0020 (6)	0.0051 (5)
O2	0.0824 (9)	0.0565 (8)	0.0942 (9)	−0.0331 (7)	0.0119 (7)	−0.0141 (7)
O3	0.0740 (9)	0.1009 (12)	0.0691 (8)	−0.0048 (8)	−0.0020 (7)	0.0225 (7)
O4	0.0705 (8)	0.0792 (10)	0.0640 (7)	0.0013 (7)	0.0155 (6)	0.0001 (7)
S1	0.0557 (3)	0.0399 (3)	0.0553 (3)	−0.00635 (19)	0.00194 (18)	−0.00117 (17)

Geometric parameters (Å, º) top

C1—C2	1.378 (2)	C8—H8	0.9300
C1—C6	1.378 (2)	C9—C10	1.326 (2)
C1—H1	0.9300	C9—H9	0.9300
C2—C3	1.359 (2)	C10—C11	1.483 (2)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.363 (3)	C11—O3	1.195 (2)
C3—H3	0.9300	C11—O4	1.319 (2)
C4—C5	1.389 (3)	C12—C13	1.451 (3)
C4—H4	0.9300	C12—O4	1.469 (2)
C5—C6	1.383 (2)	C12—H12A	0.9700
C5—H5	0.9300	C12—H12B	0.9700
C6—S1	1.7595 (15)	C13—H13A	0.9600
C7—C8	1.320 (2)	C13—H13B	0.9600
C7—S1	1.7434 (15)	C13—H13C	0.9600
C7—H7	0.9300	O1—S1	1.4294 (12)
C8—C9	1.452 (2)	O2—S1	1.4328 (13)

C2—C1—C6	119.12 (15)	C8—C9—H9	117.4
C2—C1—H1	120.4	C9—C10—C11	119.36 (17)
C6—C1—H1	120.4	C9—C10—H10	120.3
C3—C2—C1	120.67 (15)	C11—C10—H10	120.3
C3—C2—H2	119.7	O3—C11—O4	123.62 (16)
C1—C2—H2	119.7	O3—C11—C10	124.36 (17)
C2—C3—C4	120.76 (17)	O4—C11—C10	112.01 (15)
C2—C3—H3	119.6	C13—C12—O4	108.24 (19)
C4—C3—H3	119.6	C13—C12—H12A	110.1
C3—C4—C5	119.78 (17)	O4—C12—H12A	110.1
C3—C4—H4	120.1	C13—C12—H12B	110.1
C5—C4—H4	120.1	O4—C12—H12B	110.1
C6—C5—C4	119.32 (16)	H12A—C12—H12B	108.4
C6—C5—H5	120.3	C12—C13—H13A	109.5
C4—C5—H5	120.3	C12—C13—H13B	109.5
C1—C6—C5	120.34 (15)	H13A—C13—H13B	109.5
C1—C6—S1	119.90 (12)	C12—C13—H13C	109.5
C5—C6—S1	119.71 (11)	H13A—C13—H13C	109.5
C8—C7—S1	123.19 (13)	H13B—C13—H13C	109.5
C8—C7—H7	118.4	C11—O4—C12	115.52 (15)
S1—C7—H7	118.4	O1—S1—O2	119.36 (8)
C7—C8—C9	120.95 (15)	O1—S1—C7	108.53 (8)
C7—C8—H8	119.5	O2—S1—C7	107.09 (8)
C9—C8—H8	119.5	O1—S1—C6	109.53 (7)
C10—C9—C8	125.22 (16)	O2—S1—C6	108.57 (7)
C10—C9—H9	117.4	C7—S1—C6	102.40 (7)

C6—C1—C2—C3	−0.3 (3)	O3—C11—O4—C12	4.5 (3)
C1—C2—C3—C4	0.9 (3)	C10—C11—O4—C12	−176.12 (16)
C2—C3—C4—C5	−0.5 (3)	C13—C12—O4—C11	−171.7 (2)
C3—C4—C5—C6	−0.4 (3)	C8—C7—S1—O1	−4.46 (18)
C2—C1—C6—C5	−0.7 (2)	C8—C7—S1—O2	125.64 (16)
C2—C1—C6—S1	176.98 (12)	C8—C7—S1—C6	−120.23 (16)
C4—C5—C6—C1	1.0 (2)	C1—C6—S1—O1	144.75 (14)
C4—C5—C6—S1	−176.61 (14)	C5—C6—S1—O1	−37.59 (14)
S1—C7—C8—C9	−177.71 (12)	C1—C6—S1—O2	12.83 (15)
C7—C8—C9—C10	176.02 (18)	C5—C6—S1—O2	−169.51 (12)
C8—C9—C10—C11	−179.12 (15)	C1—C6—S1—C7	−100.21 (14)
C9—C10—C11—O3	−8.3 (3)	C5—C6—S1—C7	77.46 (14)
C9—C10—C11—O4	172.26 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O3ⁱ	0.93	2.32	3.212 (2)	161

Symmetry code: (i) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄O₄S
M_r	266.30
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	6.2525 (3), 7.8889 (4), 14.5049 (7)
α, β, γ (°)	82.828 (3), 87.261 (2), 72.426 (2)
V (Å³)	676.69 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.45 × 0.38 × 0.15

Data collection
Diffractometer	Bruker APEXII KappaCCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.899, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	8948, 3084, 2621
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.147, 1.87
No. of reflections	3084
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.30

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O3ⁱ	0.93	2.32	3.212 (2)	160.6

Symmetry code: (i) −x+2, −y, −z+1.

Acknowledgements

SA thanks the UGC, India, for financial support.

References

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