organic compounds
Ethyl (2E,4E)-5-(3-bromophenylsulfonyl)penta-2,4-dienoate
aDepartment of Physics, Presidency College, Chennai 600 005, India, and bDepartment of Chemistry, Pachaiyappa's College, Chennai 600 030, India
*Correspondence e-mail: aravindhanpresidency@gmail.com
In the title compound, C13H13BrO4S, both C=C double bonds adopt an E conformation. The S atom has a distorted tetrahedral geometry with bond angles ranging from 102.17 (13) to 119.77 (14)°. The ethyl acrylate substituent adopts an extented conformation with all torsion angles close to 180°. 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); Chumakov et al. (2006); Kremer et al. (2006). For related structures, see: Li et al. (2011); Sankar et al. (2012); Chakkaravarthi et al. (2008); Rodriguez et al. (1995). For graph-set analysis of hydrogen bonds, see: Sankar et al. (2012).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell 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 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).
Supporting information
10.1107/S1600536813005771/bt6881sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813005771/bt6881Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536813005771/bt6881Isup3.cml
LHMDS (6.8 ml, 7.2 mmol, 2.5 equiv, 1.06 molar solution in THF) was added drop wise to a -15 °C cooled solution of bis 3-bromo phenyl sulfonyl methane (1 g, 2.9 mmol, 1 equiv) in dried THF (15 ml) under argon atm. The reaction mixture was stirred at -15 °C for 1 h, and then trans ethyl 4-bromo crotonate (0.61 g, 3.2 mmol, 1.1 equiv) in dry THF (5 ml) was added drop wise over the period of 10 min and allow the reaction mixture to come RT over the period of 1–2 h and stirred at RT for 24 h. The reaction mixture was quenched with sat NH4Cl (20 ml) and extracted with ethyl acetate (2x20 ml) washed with water (2x20 ml) and sat brine (20 ml), the organic layer was dried over MgSO4. Evaporation of the solvent under vacuum furnished desired crude product, The residue was purified by
on silica gel (230–400 mesh) with 17–20% of ethyl acetate in hexanes afforded the corresponding product 2E,4E)-ethyl 5-(3-bromophenylsulfonyl)penta-2,4-dienoateenoate as a colourless solid.Hydrogen atoms were placed in calculated positions with C—H ranging from 0.93 Å to 0.97 Å and refined using a the riding model with fixed isotropic displacement parameters: Uiso(H) = 1.5 Ueq(C) for the methyl group and Uiso(H) = 1.2 Ueq(C) for other groups.
Data collection: APEX2 (Bruker, 2008); cell
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 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).C13H13BrO4S | F(000) = 1392 |
Mr = 345.20 | Dx = 1.592 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 5710 reflections |
a = 27.883 (5) Å | θ = 1.8–28.5° |
b = 6.001 (5) Å | µ = 3.01 mm−1 |
c = 17.256 (5) Å | T = 293 K |
β = 94.020 (5)° | Monoclinic, colourless |
V = 2880 (3) Å3 | 0.32 × 0.20 × 0.10 mm |
Z = 8 |
Bruker APEXII CCD area-detector diffractometer | 3479 independent reflections |
Radiation source: fine-focus sealed tube | 2360 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ω and ϕ scans | θmax = 28.1°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −35→36 |
Tmin = 0.972, Tmax = 0.992 | k = −7→7 |
14906 measured reflections | l = −22→22 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0677P)2 + 0.4368P] where P = (Fo2 + 2Fc2)/3 |
3479 reflections | (Δ/σ)max = 0.006 |
172 parameters | Δρmax = 0.73 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
C13H13BrO4S | V = 2880 (3) Å3 |
Mr = 345.20 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 27.883 (5) Å | µ = 3.01 mm−1 |
b = 6.001 (5) Å | T = 293 K |
c = 17.256 (5) Å | 0.32 × 0.20 × 0.10 mm |
β = 94.020 (5)° |
Bruker APEXII CCD area-detector diffractometer | 3479 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 2360 reflections with I > 2σ(I) |
Tmin = 0.972, Tmax = 0.992 | Rint = 0.035 |
14906 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.73 e Å−3 |
3479 reflections | Δρmin = −0.41 e Å−3 |
172 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.826326 (13) | 0.42424 (6) | 0.247333 (16) | 0.06505 (16) | |
S1 | 0.83626 (3) | 0.20959 (12) | −0.06349 (4) | 0.0457 (2) | |
O1 | 0.84030 (9) | 0.4471 (3) | −0.06892 (12) | 0.0624 (6) | |
O2 | 0.80643 (9) | 0.0904 (4) | −0.12028 (12) | 0.0616 (6) | |
O3 | 1.04522 (10) | −0.3791 (5) | −0.07427 (19) | 0.0914 (9) | |
C7 | 0.89422 (11) | 0.0998 (5) | −0.05976 (16) | 0.0494 (7) | |
H7 | 0.9190 | 0.1778 | −0.0331 | 0.059* | |
O4 | 1.01637 (8) | −0.6642 (5) | −0.14354 (16) | 0.0839 (8) | |
C10 | 0.96335 (12) | −0.3814 (6) | −0.1170 (2) | 0.0589 (8) | |
H10 | 0.9396 | −0.4653 | −0.1438 | 0.071* | |
C5 | 0.81767 (9) | 0.1422 (4) | 0.02920 (14) | 0.0398 (6) | |
C6 | 0.82704 (9) | 0.2916 (4) | 0.08969 (13) | 0.0411 (6) | |
H6 | 0.8414 | 0.4286 | 0.0815 | 0.049* | |
C4 | 0.79667 (11) | −0.0622 (5) | 0.04048 (17) | 0.0520 (7) | |
H4 | 0.7913 | −0.1616 | −0.0006 | 0.062* | |
C8 | 0.90412 (11) | −0.0915 (5) | −0.09374 (16) | 0.0484 (7) | |
H8 | 0.8795 | −0.1664 | −0.1220 | 0.058* | |
C11 | 1.01207 (12) | −0.4709 (6) | −0.10820 (18) | 0.0582 (8) | |
C2 | 0.79283 (10) | 0.0286 (5) | 0.17491 (17) | 0.0507 (7) | |
H2 | 0.7845 | −0.0094 | 0.2245 | 0.061* | |
C1 | 0.81425 (10) | 0.2298 (5) | 0.16221 (14) | 0.0428 (6) | |
C3 | 0.78369 (12) | −0.1169 (6) | 0.11396 (18) | 0.0585 (8) | |
H3 | 0.7687 | −0.2524 | 0.1223 | 0.070* | |
C9 | 0.95162 (11) | −0.1879 (5) | −0.08865 (16) | 0.0538 (8) | |
H9 | 0.9761 | −0.1053 | −0.0630 | 0.065* | |
C12 | 1.06419 (14) | −0.7664 (9) | −0.1426 (3) | 0.0987 (14) | |
H12A | 1.0883 | −0.6510 | −0.1460 | 0.118* | |
H12B | 1.0709 | −0.8463 | −0.0942 | 0.118* | |
C13 | 1.06654 (17) | −0.9140 (9) | −0.2053 (3) | 0.1135 (18) | |
H13B | 1.0979 | −0.9801 | −0.2039 | 0.170* | |
H13A | 1.0605 | −0.8342 | −0.2532 | 0.170* | |
H13C | 1.0428 | −1.0288 | −0.2017 | 0.170* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0838 (3) | 0.0745 (3) | 0.03659 (18) | 0.00982 (17) | 0.00276 (15) | −0.01125 (13) |
S1 | 0.0591 (5) | 0.0479 (4) | 0.0299 (3) | −0.0021 (3) | 0.0025 (3) | 0.0021 (3) |
O1 | 0.0920 (17) | 0.0469 (13) | 0.0493 (12) | 0.0012 (11) | 0.0120 (11) | 0.0132 (9) |
O2 | 0.0664 (14) | 0.0790 (16) | 0.0375 (10) | −0.0003 (11) | −0.0098 (9) | −0.0063 (9) |
O3 | 0.0638 (17) | 0.102 (2) | 0.105 (2) | −0.0017 (15) | −0.0198 (15) | −0.0347 (17) |
C7 | 0.0517 (18) | 0.0586 (19) | 0.0382 (14) | −0.0134 (14) | 0.0044 (12) | −0.0030 (12) |
O4 | 0.0497 (14) | 0.0894 (18) | 0.110 (2) | 0.0094 (13) | −0.0102 (13) | −0.0372 (16) |
C10 | 0.0491 (19) | 0.064 (2) | 0.0635 (19) | −0.0077 (15) | 0.0030 (15) | −0.0109 (15) |
C5 | 0.0440 (15) | 0.0432 (14) | 0.0321 (12) | −0.0003 (12) | 0.0023 (11) | 0.0022 (10) |
C6 | 0.0452 (16) | 0.0418 (15) | 0.0364 (13) | −0.0002 (12) | 0.0035 (11) | 0.0002 (11) |
C4 | 0.0541 (19) | 0.0563 (19) | 0.0453 (15) | −0.0129 (14) | 0.0024 (13) | −0.0016 (13) |
C8 | 0.0542 (18) | 0.0529 (17) | 0.0386 (14) | −0.0084 (14) | 0.0065 (12) | −0.0040 (12) |
C11 | 0.052 (2) | 0.070 (2) | 0.0517 (17) | −0.0072 (16) | 0.0005 (15) | −0.0075 (15) |
C2 | 0.0421 (17) | 0.068 (2) | 0.0425 (15) | 0.0031 (14) | 0.0089 (12) | 0.0115 (13) |
C1 | 0.0410 (15) | 0.0531 (16) | 0.0341 (12) | 0.0095 (13) | 0.0009 (11) | −0.0028 (11) |
C3 | 0.059 (2) | 0.063 (2) | 0.0539 (18) | −0.0192 (16) | 0.0038 (15) | 0.0145 (14) |
C9 | 0.0539 (19) | 0.062 (2) | 0.0456 (15) | −0.0123 (15) | 0.0076 (13) | −0.0103 (14) |
C12 | 0.053 (2) | 0.134 (4) | 0.107 (3) | 0.027 (2) | −0.012 (2) | −0.035 (3) |
C13 | 0.081 (3) | 0.139 (5) | 0.121 (4) | 0.045 (3) | 0.013 (3) | −0.007 (3) |
Br1—C1 | 1.888 (3) | C6—H6 | 0.9300 |
S1—O2 | 1.431 (2) | C4—C3 | 1.382 (4) |
S1—O1 | 1.433 (2) | C4—H4 | 0.9300 |
S1—C7 | 1.742 (3) | C8—C9 | 1.442 (4) |
S1—C5 | 1.763 (2) | C8—H8 | 0.9300 |
O3—C11 | 1.193 (4) | C2—C1 | 1.371 (4) |
C7—C8 | 1.327 (4) | C2—C3 | 1.377 (5) |
C7—H7 | 0.9300 | C2—H2 | 0.9300 |
O4—C11 | 1.320 (4) | C3—H3 | 0.9300 |
O4—C12 | 1.467 (4) | C9—H9 | 0.9300 |
C10—C9 | 1.310 (5) | C12—C13 | 1.403 (6) |
C10—C11 | 1.459 (5) | C12—H12A | 0.9700 |
C10—H10 | 0.9300 | C12—H12B | 0.9700 |
C5—C4 | 1.379 (4) | C13—H13B | 0.9600 |
C5—C6 | 1.387 (3) | C13—H13A | 0.9600 |
C6—C1 | 1.376 (3) | C13—H13C | 0.9600 |
O2—S1—O1 | 119.77 (14) | O3—C11—C10 | 124.4 (3) |
O2—S1—C7 | 109.23 (14) | O4—C11—C10 | 112.9 (3) |
O1—S1—C7 | 107.56 (15) | C1—C2—C3 | 119.7 (3) |
O2—S1—C5 | 108.23 (13) | C1—C2—H2 | 120.2 |
O1—S1—C5 | 108.47 (13) | C3—C2—H2 | 120.2 |
C7—S1—C5 | 102.17 (13) | C2—C1—C6 | 121.8 (2) |
C8—C7—S1 | 122.1 (2) | C2—C1—Br1 | 118.4 (2) |
C8—C7—H7 | 118.9 | C6—C1—Br1 | 119.8 (2) |
S1—C7—H7 | 118.9 | C2—C3—C4 | 120.3 (3) |
C11—O4—C12 | 118.3 (3) | C2—C3—H3 | 119.9 |
C9—C10—C11 | 122.9 (3) | C4—C3—H3 | 119.9 |
C9—C10—H10 | 118.6 | C10—C9—C8 | 125.8 (3) |
C11—C10—H10 | 118.6 | C10—C9—H9 | 117.1 |
C4—C5—C6 | 121.9 (2) | C8—C9—H9 | 117.1 |
C4—C5—S1 | 119.1 (2) | C13—C12—O4 | 110.3 (3) |
C6—C5—S1 | 118.9 (2) | C13—C12—H12A | 109.6 |
C1—C6—C5 | 117.6 (2) | O4—C12—H12A | 109.6 |
C1—C6—H6 | 121.2 | C13—C12—H12B | 109.6 |
C5—C6—H6 | 121.2 | O4—C12—H12B | 109.6 |
C5—C4—C3 | 118.8 (3) | H12A—C12—H12B | 108.1 |
C5—C4—H4 | 120.6 | C12—C13—H13B | 109.5 |
C3—C4—H4 | 120.6 | C12—C13—H13A | 109.5 |
C7—C8—C9 | 122.6 (3) | H13B—C13—H13A | 109.5 |
C7—C8—H8 | 118.7 | C12—C13—H13C | 109.5 |
C9—C8—H8 | 118.7 | H13B—C13—H13C | 109.5 |
O3—C11—O4 | 122.7 (3) | H13A—C13—H13C | 109.5 |
O2—S1—C7—C8 | −12.3 (3) | C12—O4—C11—O3 | −1.7 (6) |
O1—S1—C7—C8 | −143.8 (2) | C12—O4—C11—C10 | 176.8 (4) |
C5—S1—C7—C8 | 102.1 (3) | C9—C10—C11—O3 | 0.8 (6) |
O2—S1—C5—C4 | 28.0 (3) | C9—C10—C11—O4 | −177.7 (3) |
O1—S1—C5—C4 | 159.4 (2) | C3—C2—C1—C6 | 0.0 (4) |
C7—S1—C5—C4 | −87.1 (3) | C3—C2—C1—Br1 | −179.8 (2) |
O2—S1—C5—C6 | −155.5 (2) | C5—C6—C1—C2 | −0.2 (4) |
O1—S1—C5—C6 | −24.1 (3) | C5—C6—C1—Br1 | 179.61 (19) |
C7—S1—C5—C6 | 89.3 (2) | C1—C2—C3—C4 | 1.0 (5) |
C4—C5—C6—C1 | −0.5 (4) | C5—C4—C3—C2 | −1.7 (5) |
S1—C5—C6—C1 | −176.9 (2) | C11—C10—C9—C8 | −178.6 (3) |
C6—C5—C4—C3 | 1.5 (5) | C7—C8—C9—C10 | 176.0 (3) |
S1—C5—C4—C3 | 177.8 (2) | C11—O4—C12—C13 | −156.5 (4) |
S1—C7—C8—C9 | −177.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O3i | 0.93 | 2.37 | 3.235 (4) | 154 |
Symmetry code: (i) −x+2, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C13H13BrO4S |
Mr | 345.20 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 27.883 (5), 6.001 (5), 17.256 (5) |
β (°) | 94.020 (5) |
V (Å3) | 2880 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 3.01 |
Crystal size (mm) | 0.32 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.972, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14906, 3479, 2360 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.662 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.116, 1.01 |
No. of reflections | 3479 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.73, −0.41 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O3i | 0.93 | 2.37 | 3.235 (4) | 154.2 |
Symmetry code: (i) −x+2, −y, −z. |
Acknowledgements
SA and VS thank the UGC, India, for financial support. The authors thank Dr Babu Varghese, Senior Scientific Officer, SAIF, IIT, Chennai, India, for the
data collection.References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Phenyl sulfonyl containing compounds show a wide range of biological properties (De-Benedetti et al., 1985). Sulfonamide derivatives are extensively used in medicine as they possess a wide range of medicinal, pharmacological and antimicrobial properties (Chumakov et al., 2006, Kremer et al., 2006).
Fig.1. shows a displacement ellipsoid plot of the title compound. The geometric parameters of the molecule of (I) (Fig. 1) agree well with the reported values of similar structures (Sankar et al., 2012). Both C=C double bonds display an E configuration. The title molecule exhibits structural similarities with the already reported related structures (Li et al., 2011; Sankar, et al., 2012). The dihedral angle between two planes (C6—C5—S1—O1) and (C4—C5—S1—O2) is 35.30 (13)°. The torsion angles C6—C5—S1-O1 and C4—C5—S1—O2 [-24.1 (2)° and 28 (2)°, respectively] indicate syn-conformation of the sulfonyl moiety. The S atom exhibits significant deviation from a regular tetrahedron, with the largest deviations being seen for the O1—S1—O2 [119.77 (14)°] and C5—S1—C7 [102.17 (13)°] angles. The widening of the angles may be due to repulsive interactions between the two short S=O bonds, similar to what is observed in related structures (Chakkaravarthi et al., 2008; Rodriguez et al., 1995). The ethyl acrylate group substituted at C7 position of the phenyl sulfonyl takes up an extented conformation which is evident from the torsion angle values [C8—C9—C10—C11 =] -178.6 (2)°; [C9—C10—C11—O3 =] 0.9 (3)°; [C9—C10—C11—O4 =]- 177.5 (2)°; [C10—C11—O4—C12 =]176.7 [C11—O4—C12—C13=] -156.6 (2)°.
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.