Literature DB >> 21202709

(2E)-2-(2,4-Dichloro-phenyl-sulfon-yl)-3-(3-methoxy-anilino)-3-(methyl-sulfan-yl)acrylonitrile.

Mario V Capparelli, Arthur R Barazarte, Jaime E Charris.   

Abstract

The title compound, C(17)H(14)Cl(2)N(2)O(3)S(2), and the 4-methyl-anilino analogue reported in the following paper have been used as starting materials to develop benzothia-zine derivatives with anti-malarial activity. The mol-ecule displays an E (trans) configuration about the central double bond. Due to conjugation in the C=C-C N group, the putative single bond shows a significant shortening [1.421 (3) Å]. The mol-ecule has a six-membered ring involving an intra-molecular N-H⋯O(sulfon-yl) bond, which is an example of resonance-assisted hydrogen bonding. There is also an intra-molecular N-H⋯Cl hydrogen bond. In the crystal structure, bonds of the C-H⋯O(sulfon-yl) type form chains that run along [101], while N-H⋯O(sulfon-yl) bonds connect centrosymmetrically related molecules in pairs of these chains, forming ribbons. Comparison of the N⋯O distances in the intra- and inter-molecular N-H⋯O(sulfon-yl) bonds reveals that the π-bond co-operativity results in a strengthening of the intra-molecular hydrogen bond. There are also π-π inter-actions between benzene rings of pairs of centrosymmetrically related mol-ecules [centroid-centroid distance = 3.8612 (13) Å], as well as C-H⋯π interactions.

Entities:  

Year:  2008        PMID： 21202709      PMCID： PMC2961343          DOI： 10.1107/S160053680801252X

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For related literature, see: Allen (2002 ▶); Allen et al. (1987 ▶); Baraza­rte et al. (2008 ▶); Capparelli et al. (2008 ▶); Charris et al. (2005 ▶, 2007 ▶); Gilli et al. (1989 ▶); Kennard et al. (2003 ▶); Krivokolysko et al. (2002 ▶); Song et al. (2005 ▶); Tominaga et al. (1989 ▶, 2002 ▶).

Experimental

Crystal data

C17H14Cl2N2O3S2 M = 429.32 Monoclinic, a = 11.6125 (7) Å b = 10.1419 (6) Å c = 16.4048 (10) Å β = 100.926 (1)° V = 1897.0 (2) Å3 Z = 4 Mo Kα radiation μ = 0.58 mm−1 T = 296 (2) K 0.29 × 0.22 × 0.17 mm

Data collection

Bruker SMART APEX diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.796, T max = 0.906 12828 measured reflections 4659 independent reflections 3653 reflections with I > 2σ(I) R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.044 wR(F 2) = 0.119 S = 1.04 4659 reflections 237 parameters H-atom parameters constrained Δρmax = 0.58 e Å−3 Δρmin = −0.27 e Å−3 Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2003 ▶). Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680801252X/bg2184sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S160053680801252X/bg2184Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C17H14Cl2N2O3S2F000 = 880
Mr = 429.32Dx = 1.503 Mg m−3
Monoclinic, P21/nMelting point = 409–411 K
Hall symbol: -P 2ynMo Kα radiation λ = 0.71073 Å
a = 11.6125 (7) ÅCell parameters from 3492 reflections
b = 10.1419 (6) Åθ = 2.4–28.1º
c = 16.4048 (10) ŵ = 0.58 mm−1
β = 100.926 (1)ºT = 296 (2) K
V = 1897.0 (2) Å3Prism, colourless
Z = 40.29 × 0.22 × 0.17 mm
Bruker SMART APEX diffractometer4659 independent reflections
Radiation source: fine-focus sealed tube3653 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.024
Detector resolution: 8.13 pixels mm-1θmax = 29.1º
T = 296(2) Kθmin = 2.0º
φ and ω scansh = −13→15
Absorption correction: multi-scan(SADABS; Bruker, 2001)k = −13→13
Tmin = 0.796, Tmax = 0.906l = −22→15
12828 measured reflections
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.119  w = 1/[σ2(Fo2) + (0.0578P)2 + 0.5461P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
4659 reflectionsΔρmax = 0.58 e Å−3
237 parametersΔρmin = −0.27 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
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.
xyzUiso*/Ueq
S10.77042 (4)0.46268 (5)0.02088 (3)0.03340 (13)
S20.90726 (5)0.19039 (6)0.21790 (4)0.05277 (17)
Cl10.95425 (5)0.66027 (6)0.13868 (5)0.0661 (2)
Cl20.62331 (7)1.02603 (7)0.11885 (6)0.0852 (3)
O10.66548 (12)0.40951 (15)−0.02832 (9)0.0479 (4)
O20.87384 (12)0.46887 (14)−0.01526 (9)0.0422 (3)
O31.2713 (2)−0.0272 (2)0.10486 (15)0.0869 (7)
N10.62151 (18)0.3565 (3)0.17764 (15)0.0692 (6)
N21.01127 (14)0.34675 (17)0.11897 (11)0.0432 (4)
H21.00730.41570.08800.052*
C110.73323 (15)0.62359 (19)0.04938 (11)0.0337 (4)
C120.81194 (16)0.7078 (2)0.09891 (13)0.0395 (4)
C130.77859 (19)0.8317 (2)0.11955 (14)0.0462 (5)
H130.83140.88720.15290.055*
C140.6645 (2)0.8717 (2)0.08946 (15)0.0500 (5)
C150.58494 (19)0.7912 (2)0.04044 (15)0.0524 (6)
H150.50860.82000.02140.063*
C160.61911 (17)0.6676 (2)0.01975 (13)0.0425 (5)
H160.56590.6132−0.01410.051*
C211.12266 (16)0.2827 (2)0.13590 (12)0.0381 (4)
C221.13568 (19)0.1547 (2)0.11007 (13)0.0462 (5)
H221.07150.10740.08220.055*
C231.2473 (2)0.0979 (2)0.12682 (15)0.0534 (6)
C241.3416 (2)0.1696 (3)0.16728 (16)0.0594 (7)
H241.41560.13110.17870.071*
C251.3275 (2)0.2962 (3)0.19075 (16)0.0573 (6)
H251.39210.34410.21740.069*
C261.21789 (19)0.3539 (2)0.17530 (14)0.0479 (5)
H261.20850.44060.19140.058*
C10.70534 (17)0.3590 (2)0.15151 (13)0.0433 (5)
C20.80432 (16)0.37253 (19)0.11286 (12)0.0352 (4)
C30.91295 (16)0.31489 (19)0.14429 (12)0.0351 (4)
C41.0420 (2)0.1996 (3)0.29231 (15)0.0709 (8)
H4B1.10410.16070.26920.106*
H4C1.03360.15270.34170.106*
H4A1.06040.29020.30580.106*
C51.1784 (4)−0.1029 (4)0.0621 (3)0.1160 (15)
H5B1.1195−0.11230.09560.174*
H5C1.2069−0.18840.05060.174*
H5A1.1452−0.05990.01090.174*
U11U22U33U12U13U23
S10.0278 (2)0.0382 (3)0.0323 (2)0.00214 (17)0.00072 (17)−0.00024 (18)
S20.0432 (3)0.0603 (4)0.0538 (3)0.0042 (2)0.0066 (2)0.0228 (3)
Cl10.0329 (3)0.0604 (4)0.0935 (5)0.0095 (2)−0.0169 (3)−0.0257 (3)
Cl20.0768 (5)0.0594 (4)0.1172 (7)0.0303 (3)0.0126 (4)−0.0190 (4)
O10.0398 (8)0.0511 (9)0.0462 (8)−0.0016 (7)−0.0088 (6)−0.0057 (7)
O20.0385 (7)0.0509 (8)0.0386 (8)0.0085 (6)0.0112 (6)0.0056 (6)
O30.0812 (14)0.0708 (13)0.1052 (17)0.0331 (11)0.0093 (12)−0.0160 (12)
N10.0398 (11)0.1008 (18)0.0705 (15)0.0078 (11)0.0196 (10)0.0213 (13)
N20.0305 (8)0.0460 (9)0.0531 (10)0.0094 (7)0.0075 (7)0.0172 (8)
C110.0270 (8)0.0384 (10)0.0349 (10)0.0035 (7)0.0041 (7)0.0024 (7)
C120.0291 (9)0.0442 (11)0.0435 (11)0.0048 (8)0.0024 (8)−0.0011 (8)
C130.0438 (11)0.0434 (12)0.0505 (13)0.0021 (9)0.0063 (9)−0.0060 (9)
C140.0502 (13)0.0426 (12)0.0590 (14)0.0156 (10)0.0149 (11)0.0019 (10)
C150.0348 (11)0.0563 (14)0.0642 (15)0.0155 (10)0.0045 (10)0.0072 (11)
C160.0294 (10)0.0494 (12)0.0459 (12)0.0042 (8)0.0002 (8)0.0047 (9)
C210.0315 (9)0.0460 (11)0.0371 (10)0.0083 (8)0.0070 (8)0.0083 (8)
C220.0419 (11)0.0503 (12)0.0445 (12)0.0029 (9)0.0036 (9)0.0009 (9)
C230.0580 (14)0.0526 (13)0.0506 (13)0.0206 (11)0.0126 (11)0.0014 (10)
C240.0366 (12)0.0815 (19)0.0593 (15)0.0201 (11)0.0074 (10)0.0067 (13)
C250.0351 (11)0.0728 (16)0.0597 (15)0.0007 (11)−0.0020 (10)0.0049 (12)
C260.0393 (11)0.0524 (13)0.0502 (13)0.0033 (9)0.0038 (9)0.0023 (10)
C10.0321 (10)0.0517 (12)0.0447 (12)0.0028 (9)0.0040 (8)0.0096 (9)
C20.0285 (9)0.0408 (10)0.0358 (10)0.0011 (7)0.0045 (7)0.0041 (8)
C30.0309 (9)0.0383 (10)0.0347 (10)0.0012 (7)0.0031 (7)0.0023 (8)
C40.0549 (15)0.113 (2)0.0428 (13)0.0180 (15)0.0042 (11)0.0260 (14)
C50.118 (3)0.073 (2)0.150 (4)0.002 (2)0.009 (3)−0.040 (2)
S1—O11.4333 (14)C15—H150.9300
S1—O21.4380 (14)C16—H160.9300
S1—C21.7443 (19)C21—C261.375 (3)
S1—C111.7733 (19)C21—C221.383 (3)
S2—C31.757 (2)C22—C231.397 (3)
S2—C41.795 (3)C22—H220.9300
Cl1—C121.7264 (19)C23—C241.375 (4)
Cl2—C141.732 (2)C24—C251.359 (4)
O3—C231.362 (3)C24—H240.9300
O3—C51.399 (4)C25—C261.380 (3)
N1—C11.136 (3)C25—H250.9300
N2—C31.327 (2)C26—H260.9300
N2—C211.427 (2)C1—C21.421 (3)
N2—H20.8600C2—C31.397 (3)
C11—C121.394 (3)C4—H4B0.9600
C11—C161.396 (2)C4—H4C0.9600
C12—C131.376 (3)C4—H4A0.9600
C13—C141.384 (3)C5—H5B0.9600
C13—H130.9300C5—H5C0.9600
C14—C151.373 (3)C5—H5A0.9600
C15—C161.377 (3)
O1—S1—O2118.14 (9)C21—C22—H22120.7
O1—S1—C2108.56 (9)C23—C22—H22120.7
O2—S1—C2108.08 (9)O3—C23—C24115.9 (2)
O1—S1—C11105.74 (9)O3—C23—C22124.1 (2)
O2—S1—C11109.43 (9)C24—C23—C22120.1 (2)
C2—S1—C11106.30 (9)C25—C24—C23120.6 (2)
C3—S2—C4106.78 (12)C25—C24—H24119.7
C23—O3—C5117.8 (2)C23—C24—H24119.7
C3—N2—C21129.07 (17)C24—C25—C26120.3 (2)
C3—N2—H2115.5C24—C25—H25119.8
C21—N2—H2115.5C26—C25—H25119.8
C12—C11—C16118.77 (18)C21—C26—C25119.7 (2)
C12—C11—S1123.49 (14)C21—C26—H26120.2
C16—C11—S1117.73 (15)C25—C26—H26120.2
C13—C12—C11121.26 (18)N1—C1—C2173.9 (2)
C13—C12—Cl1117.11 (16)C3—C2—C1123.04 (18)
C11—C12—Cl1121.62 (15)C3—C2—S1125.34 (15)
C12—C13—C14118.3 (2)C1—C2—S1111.57 (14)
C12—C13—H13120.8N2—C3—C2123.57 (17)
C14—C13—H13120.8N2—C3—S2122.47 (14)
C15—C14—C13121.8 (2)C2—C3—S2113.91 (14)
C15—C14—Cl2120.62 (17)S2—C4—H4B109.5
C13—C14—Cl2117.50 (18)S2—C4—H4C109.5
C14—C15—C16119.48 (19)H4B—C4—H4C109.5
C14—C15—H15120.3S2—C4—H4A109.5
C16—C15—H15120.3H4B—C4—H4A109.5
C15—C16—C11120.3 (2)H4C—C4—H4A109.5
C15—C16—H16119.8O3—C5—H5B109.5
C11—C16—H16119.8O3—C5—H5C109.5
C26—C21—C22120.81 (19)H5B—C5—H5C109.5
C26—C21—N2118.09 (19)O3—C5—H5A109.5
C22—C21—N2121.03 (18)H5B—C5—H5A109.5
C21—C22—C23118.5 (2)H5C—C5—H5A109.5
O1—S1—C11—C12179.07 (17)C5—O3—C23—C220.7 (4)
O2—S1—C11—C12−52.70 (19)C21—C22—C23—O3179.8 (2)
C2—S1—C11—C1263.80 (19)C21—C22—C23—C24−0.8 (3)
O1—S1—C11—C16−1.47 (18)O3—C23—C24—C25179.0 (2)
O2—S1—C11—C16126.77 (16)C22—C23—C24—C25−0.5 (4)
C2—S1—C11—C16−116.74 (16)C23—C24—C25—C260.9 (4)
C16—C11—C12—C130.8 (3)C22—C21—C26—C25−1.3 (3)
S1—C11—C12—C13−179.76 (17)N2—C21—C26—C25−178.4 (2)
C16—C11—C12—Cl1179.47 (16)C24—C25—C26—C210.0 (4)
S1—C11—C12—Cl1−1.1 (3)O1—S1—C2—C3128.18 (18)
C11—C12—C13—C14−0.4 (3)O2—S1—C2—C3−1.1 (2)
Cl1—C12—C13—C14−179.12 (18)C11—S1—C2—C3−118.48 (18)
C12—C13—C14—C150.3 (4)O1—S1—C2—C1−49.26 (17)
C12—C13—C14—Cl2178.07 (18)O2—S1—C2—C1−178.53 (15)
C13—C14—C15—C16−0.6 (4)C11—S1—C2—C164.08 (17)
Cl2—C14—C15—C16−178.30 (18)C21—N2—C3—C2−169.2 (2)
C14—C15—C16—C111.0 (3)C21—N2—C3—S28.0 (3)
C12—C11—C16—C15−1.1 (3)C1—C2—C3—N2−166.4 (2)
S1—C11—C16—C15179.43 (17)S1—C2—C3—N216.5 (3)
C3—N2—C21—C26−120.4 (2)C1—C2—C3—S216.2 (3)
C3—N2—C21—C2262.5 (3)S1—C2—C3—S2−160.99 (12)
C26—C21—C22—C231.7 (3)C4—S2—C3—N237.0 (2)
N2—C21—C22—C23178.65 (19)C4—S2—C3—C2−145.56 (17)
C5—O3—C23—C24−178.8 (3)
D—H···AD—HH···AD···AD—H···A
N2—H2···O20.862.142.756 (2)129
N2—H2···O2i0.862.313.005 (2)138
N2—H2···Cl10.862.723.2763 (18)123
C4—H4C···O1ii0.962.463.215 (3)135
C16—H16···O10.932.402.815 (3)107
C4—H4B···Cg20.962.743.501 (3)137
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
N2—H2⋯O20.862.142.756 (2)129
N2—H2⋯O2i0.862.313.005 (2)138
N2—H2⋯Cl10.862.723.2763 (18)123
C4—H4C⋯O1ii0.962.463.215 (3)135
C4—H4B⋯Cg20.962.743.501 (3)137

Symmetry codes: (i) ; (ii) . Cg2 is the centroid of the C21–C26 ring.

  4 in total

1.  The Cambridge Structural Database: a quarter of a million crystal structures and rising.

Authors:  Frank H Allen
Journal:  Acta Crystallogr B       Date:  2002-05-29

2.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

3.  Synthesis, antimalarial activity, structure-activity relationship analysis of thieno-[3,2-b]benzothiazine S,S-dioxide analogs.

Authors:  Arthur Barazarte; José Camacho; José Domínguez; Gricela Lobo; Neira Gamboa; Juan Rodrigues; Mario V Capparelli; Angel Alvarez-Larena; Sebastian Andujar; Daniel Enriz; Jaime Charris
Journal:  Bioorg Med Chem       Date:  2008-02-08       Impact factor: 3.641

4.  (2E)-2-(2,4-Dichloro-phenyl-sulfon-yl)-3-(4-methyl-anilino)-3-(methyl-sulfan-yl)acrylonitrile.

Authors:  Mario V Capparelli; Arthur R Barazarte; Jaime E Charris
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2008-05-03
  4 in total
  1 in total

1.  (2E)-2-(2,4-Dichloro-phenyl-sulfon-yl)-3-(4-methyl-anilino)-3-(methyl-sulfan-yl)acrylonitrile.

Authors:  Mario V Capparelli; Arthur R Barazarte; Jaime E Charris
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2008-05-03
  1 in total

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