organic compounds
3′,4′-Diphenyl-3H,4′H-spiro[benzo[b]thiophene-2,5′-isoxazol]-3-one
aLaboratoire de Chimie Organique, Faculté des Sciences Dhar El Mahraz, Université Sidi Mohamed Ben Abdellah, BP 1796, 30000 Fès, Morocco, and bLaboratoire de Chimie Appliquée des Matériaux, Centres des Sciences des Matériaux, Faculty of Sciences, Mohammed V University in Rabat, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
*Correspondence e-mail: bakhouch_m@yahoo.com
The molecule of the title compound, C22H15NO2S, is built up from a benzothiophene system linked to an isoxazoline ring which is connected to two phenyl rings. The benzothiophene system is essentially planar, while the isoxazoline ring displays an with the spiro C atom as the flap. The mean plane through the isoxazoline ring is slightly inclined to one phenyl ring by 5.74 (13)° and is approximately perpendicular [86.10 (10)°] to the fused ring system and to the other phenyl ring [84.31 (12)°]. In the crystal, molecules are linked together by C—H⋯O hydrogen bonds and by π–π interactions between the fused ring systems [intercentroid distance = 3.702 (2) Å], forming a three-dimensional network.
Keywords: crystal structutre; diphenyl; spiroisoxazolines; isoxazoline; hydrogen bonds; π–π interactions.
CCDC reference: 1855760
Structure description
Molecules containing an isoxazoline framework have been widely used as key building blocks for medicines. Among these compounds, spiroisoxazolines have shown strong bioactivities (Bennani et al., 2007; Al Houari et al., 2008; Hwang et al., 2005). For many years, our laboratory has accumulated much experience in the design and synthesis of heterocyclic systems with isoxazoline and pyrazoline rings through 1,3-dipolar cycloaddition and cyclocondensation reactions (El Yazidi et al., 2003; Bakhouch et al., 2014, 2015, 2017; Mahfoud et al., 2015). In a continuation of our previous work, and in an attempt to evaluate the reactivity of thioaurones with as a dipole (Boughaleb et al., 2011), we describe herein the reaction of (Z)-2-benzylidenbenzo[b]thiophen-3(2H)-one with benzonitrile oxide in chloroform at low temperature. The title compound was obtained by regiospecific 1,3-dipolar cycloaddition. The results of the X-ray study were in perfect agreement with IR, 1H NMR and 13C NMR spectroscopic analysis, which confirms the regiospecificity of the reaction.
The isoxazoline ring is linked to two phenyl rings and to a benzothiophene ring system, as shown in Fig. 1. The five-membred ring (N1/O1/C8–C10) adopts an with the spiro C8 atom as the flap. The total puckering amplitude for this ring is Q2 = 0.239 (2) Å and the spherical polar angle φ2 = 137.2 (5)° (Cremer & Pople, 1975). The benzothiophene system is nearly perpendicular to the mean plane through the isoxazoline ring (N1/O1/C8–C10) and to the C11–C16 phenyl ring, as indicated by the dihedral angles of 86.10 (10) and 87.46 (11)°, respectively, between them. The dihedral angle between the fused ring system and the C17–C22 phenyl ring is 65.80 (11)°.
In the crystal, molecules are linked together by C9—H9⋯O1ii and C19—H19⋯O2i hydrogen bonds and by π–π interactions between inversion-related benzene rings of adjacent benzothiophene ring systems [intercentroid distance = 3.702 (2) Å] to form a three-dimensional network (Fig. 2 and Table 1).
Synthesis and crystallization
In a 100 ml flask, 2 mmol of (Z)-2-benzylidenebenzo[b]thiophen-3-one and 2.2 mmol of benzonitrile oxide were dissolved in 20 ml of chloroform. The mixture was cooled to 273 K under magnetic stirring in an ice bath. Then 15 ml of bleach (NaOCl, 24%) was added drop-by-drop without exceeding a temperature of 278 K. The mixture was left stirring for 4 h at room temperature, washed with water until the pH was neutral and dried over sodium sulfate (Na2SO4). The solvent was then removed under reduced pressure and the resulting residue was crystallized from ethanol (yield: 90%; m.p. 495 K). Colourless block-like crystals were obtained by slow evaporation of the ethanolic solution.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1855760
https://doi.org/10.1107/S2414314618010192/sj4187sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618010192/sj4187Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314618010192/sj4187Isup3.cml
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2016 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).C22H15NO2S | Dx = 1.372 Mg m−3 |
Mr = 357.41 | Melting point: 495 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2650 (2) Å | Cell parameters from 3811 reflections |
b = 10.3523 (2) Å | θ = 3.0–27.1° |
c = 36.0698 (8) Å | µ = 0.20 mm−1 |
V = 3459.60 (13) Å3 | T = 296 K |
Z = 8 | Block, colourless |
F(000) = 1488 | 0.35 × 0.28 × 0.25 mm |
Bruker X8 APEX diffractometer | 3811 independent reflections |
Radiation source: fine-focus sealed tube | 2597 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.089 |
φ and ω scans | θmax = 27.1°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −11→11 |
Tmin = 0.639, Tmax = 0.747 | k = −13→13 |
76407 measured reflections | l = −46→46 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.105 | w = 1/[σ2(Fo2) + (0.0215P)2 + 2.5234P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
3811 reflections | Δρmax = 0.18 e Å−3 |
235 parameters | Δρmin = −0.26 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2409 (3) | 0.4525 (2) | 0.52031 (6) | 0.0450 (5) | |
C2 | 0.2733 (3) | 0.4617 (3) | 0.48281 (7) | 0.0620 (7) | |
H2 | 0.351287 | 0.510587 | 0.474656 | 0.074* | |
C3 | 0.1865 (4) | 0.3962 (3) | 0.45792 (7) | 0.0750 (9) | |
H3 | 0.207713 | 0.400469 | 0.432749 | 0.090* | |
C4 | 0.0696 (4) | 0.3248 (3) | 0.46947 (7) | 0.0739 (9) | |
H4 | 0.012838 | 0.282128 | 0.452088 | 0.089* | |
C5 | 0.0360 (3) | 0.3160 (2) | 0.50654 (7) | 0.0559 (7) | |
H5 | −0.043069 | 0.268137 | 0.514492 | 0.067* | |
C6 | 0.1239 (2) | 0.3807 (2) | 0.53187 (6) | 0.0399 (5) | |
C7 | 0.1038 (2) | 0.3808 (2) | 0.57209 (6) | 0.0386 (5) | |
C8 | 0.2164 (2) | 0.4696 (2) | 0.59144 (6) | 0.0372 (5) | |
C9 | 0.2811 (2) | 0.40827 (19) | 0.62647 (5) | 0.0338 (4) | |
H9 | 0.274619 | 0.313886 | 0.625187 | 0.041* | |
C10 | 0.1760 (2) | 0.4606 (2) | 0.65481 (6) | 0.0361 (5) | |
C11 | 0.1605 (2) | 0.4157 (2) | 0.69323 (6) | 0.0414 (5) | |
C12 | 0.0655 (3) | 0.4780 (3) | 0.71734 (7) | 0.0623 (7) | |
H12 | 0.010973 | 0.547609 | 0.708966 | 0.075* | |
C13 | 0.0521 (4) | 0.4369 (3) | 0.75341 (8) | 0.0802 (10) | |
H13 | −0.010154 | 0.480009 | 0.769415 | 0.096* | |
C14 | 0.1291 (4) | 0.3337 (3) | 0.76594 (8) | 0.0788 (10) | |
H14 | 0.118796 | 0.306354 | 0.790355 | 0.095* | |
C15 | 0.2214 (3) | 0.2704 (3) | 0.74268 (7) | 0.0706 (8) | |
H15 | 0.273459 | 0.199575 | 0.751241 | 0.085* | |
C16 | 0.2378 (3) | 0.3114 (2) | 0.70626 (6) | 0.0519 (6) | |
H16 | 0.301303 | 0.268334 | 0.690577 | 0.062* | |
C17 | 0.4353 (2) | 0.4498 (2) | 0.63469 (6) | 0.0370 (5) | |
C22 | 0.4642 (2) | 0.5692 (2) | 0.65033 (7) | 0.0491 (6) | |
H22 | 0.388181 | 0.622907 | 0.657125 | 0.059* | |
C21 | 0.6048 (3) | 0.6096 (3) | 0.65596 (8) | 0.0665 (8) | |
H21 | 0.623101 | 0.689521 | 0.666765 | 0.080* | |
C20 | 0.7171 (3) | 0.5314 (3) | 0.64558 (8) | 0.0731 (9) | |
H20 | 0.811760 | 0.558786 | 0.649034 | 0.088* | |
C19 | 0.6900 (3) | 0.4130 (3) | 0.63010 (8) | 0.0670 (8) | |
H19 | 0.766504 | 0.360381 | 0.623001 | 0.080* | |
C18 | 0.5501 (2) | 0.3713 (3) | 0.62498 (7) | 0.0506 (6) | |
H18 | 0.532736 | 0.290003 | 0.614950 | 0.061* | |
N1 | 0.1012 (2) | 0.55663 (18) | 0.64309 (5) | 0.0452 (5) | |
O1 | 0.13553 (17) | 0.58038 (14) | 0.60528 (4) | 0.0479 (4) | |
O2 | 0.01376 (18) | 0.32410 (17) | 0.58958 (4) | 0.0573 (5) | |
S1 | 0.34013 (7) | 0.52549 (7) | 0.55640 (2) | 0.05418 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0463 (12) | 0.0488 (13) | 0.0398 (12) | 0.0096 (11) | 0.0056 (11) | 0.0066 (10) |
C2 | 0.0635 (17) | 0.0751 (18) | 0.0475 (14) | 0.0168 (15) | 0.0149 (13) | 0.0167 (14) |
C3 | 0.111 (3) | 0.081 (2) | 0.0328 (13) | 0.029 (2) | 0.0067 (16) | 0.0039 (14) |
C4 | 0.114 (3) | 0.0680 (18) | 0.0396 (14) | 0.0096 (19) | −0.0178 (17) | −0.0058 (13) |
C5 | 0.0714 (18) | 0.0473 (14) | 0.0489 (14) | −0.0008 (13) | −0.0141 (13) | −0.0007 (11) |
C6 | 0.0481 (13) | 0.0367 (11) | 0.0350 (11) | 0.0038 (10) | −0.0022 (10) | 0.0007 (9) |
C7 | 0.0374 (11) | 0.0405 (12) | 0.0379 (11) | 0.0005 (10) | −0.0016 (10) | 0.0003 (9) |
C8 | 0.0348 (11) | 0.0393 (11) | 0.0376 (11) | −0.0020 (9) | 0.0025 (9) | −0.0007 (9) |
C9 | 0.0326 (10) | 0.0323 (10) | 0.0366 (11) | 0.0000 (9) | 0.0026 (9) | −0.0011 (9) |
C10 | 0.0280 (10) | 0.0414 (12) | 0.0388 (11) | −0.0031 (9) | 0.0007 (9) | −0.0058 (9) |
C11 | 0.0347 (11) | 0.0504 (13) | 0.0390 (12) | −0.0098 (10) | 0.0047 (10) | −0.0072 (10) |
C12 | 0.0607 (16) | 0.0700 (17) | 0.0562 (15) | −0.0021 (14) | 0.0218 (13) | −0.0079 (13) |
C13 | 0.089 (2) | 0.096 (2) | 0.0560 (18) | −0.016 (2) | 0.0363 (17) | −0.0151 (17) |
C14 | 0.093 (2) | 0.104 (3) | 0.0394 (15) | −0.031 (2) | 0.0116 (16) | 0.0003 (16) |
C15 | 0.080 (2) | 0.084 (2) | 0.0477 (15) | −0.0050 (17) | −0.0041 (15) | 0.0108 (14) |
C16 | 0.0511 (14) | 0.0647 (16) | 0.0398 (12) | −0.0006 (12) | 0.0003 (12) | −0.0028 (11) |
C17 | 0.0301 (10) | 0.0436 (12) | 0.0371 (11) | 0.0017 (9) | 0.0014 (9) | 0.0076 (9) |
C22 | 0.0386 (12) | 0.0511 (14) | 0.0577 (15) | −0.0033 (11) | −0.0040 (11) | 0.0001 (11) |
C21 | 0.0526 (16) | 0.0736 (18) | 0.0733 (19) | −0.0251 (15) | −0.0138 (15) | 0.0095 (15) |
C20 | 0.0347 (14) | 0.106 (3) | 0.078 (2) | −0.0182 (16) | −0.0103 (14) | 0.0378 (19) |
C19 | 0.0351 (13) | 0.094 (2) | 0.0723 (19) | 0.0148 (14) | 0.0112 (13) | 0.0296 (17) |
C18 | 0.0408 (12) | 0.0587 (15) | 0.0522 (14) | 0.0094 (11) | 0.0071 (11) | 0.0090 (12) |
N1 | 0.0402 (10) | 0.0518 (12) | 0.0435 (11) | 0.0055 (9) | 0.0003 (9) | −0.0080 (9) |
O1 | 0.0543 (10) | 0.0428 (9) | 0.0467 (9) | 0.0107 (7) | −0.0041 (8) | −0.0014 (7) |
O2 | 0.0514 (10) | 0.0706 (11) | 0.0499 (10) | −0.0228 (9) | 0.0048 (8) | 0.0013 (9) |
S1 | 0.0460 (3) | 0.0679 (4) | 0.0486 (3) | −0.0160 (3) | 0.0036 (3) | 0.0130 (3) |
C1—C6 | 1.379 (3) | C11—C12 | 1.396 (3) |
C1—C2 | 1.389 (3) | C12—C13 | 1.374 (4) |
C1—S1 | 1.763 (2) | C12—H12 | 0.9300 |
C2—C3 | 1.383 (4) | C13—C14 | 1.362 (4) |
C2—H2 | 0.9300 | C13—H13 | 0.9300 |
C3—C4 | 1.376 (4) | C14—C15 | 1.366 (4) |
C3—H3 | 0.9300 | C14—H14 | 0.9300 |
C4—C5 | 1.376 (4) | C15—C16 | 1.389 (3) |
C4—H4 | 0.9300 | C15—H15 | 0.9300 |
C5—C6 | 1.395 (3) | C16—H16 | 0.9300 |
C5—H5 | 0.9300 | C17—C18 | 1.383 (3) |
C6—C7 | 1.463 (3) | C17—C22 | 1.385 (3) |
C7—O2 | 1.199 (2) | C22—C21 | 1.383 (3) |
C7—C8 | 1.555 (3) | C22—H22 | 0.9300 |
C8—O1 | 1.459 (2) | C21—C20 | 1.370 (4) |
C8—C9 | 1.536 (3) | C21—H21 | 0.9300 |
C8—S1 | 1.802 (2) | C20—C19 | 1.371 (4) |
C9—C10 | 1.512 (3) | C20—H20 | 0.9300 |
C9—C17 | 1.521 (3) | C19—C18 | 1.379 (4) |
C9—H9 | 0.9800 | C19—H19 | 0.9300 |
C10—N1 | 1.283 (3) | C18—H18 | 0.9300 |
C10—C11 | 1.469 (3) | N1—O1 | 1.421 (2) |
C11—C16 | 1.378 (3) | ||
C6—C1—C2 | 120.1 (2) | C12—C11—C10 | 120.2 (2) |
C6—C1—S1 | 114.68 (16) | C13—C12—C11 | 120.2 (3) |
C2—C1—S1 | 125.2 (2) | C13—C12—H12 | 119.9 |
C3—C2—C1 | 118.2 (3) | C11—C12—H12 | 119.9 |
C3—C2—H2 | 120.9 | C14—C13—C12 | 120.7 (3) |
C1—C2—H2 | 120.9 | C14—C13—H13 | 119.7 |
C4—C3—C2 | 121.6 (2) | C12—C13—H13 | 119.7 |
C4—C3—H3 | 119.2 | C13—C14—C15 | 120.1 (3) |
C2—C3—H3 | 119.2 | C13—C14—H14 | 120.0 |
C5—C4—C3 | 120.5 (3) | C15—C14—H14 | 120.0 |
C5—C4—H4 | 119.7 | C14—C15—C16 | 120.2 (3) |
C3—C4—H4 | 119.7 | C14—C15—H15 | 119.9 |
C4—C5—C6 | 118.2 (3) | C16—C15—H15 | 119.9 |
C4—C5—H5 | 120.9 | C11—C16—C15 | 120.4 (2) |
C6—C5—H5 | 120.9 | C11—C16—H16 | 119.8 |
C1—C6—C5 | 121.3 (2) | C15—C16—H16 | 119.8 |
C1—C6—C7 | 113.6 (2) | C18—C17—C22 | 118.6 (2) |
C5—C6—C7 | 125.2 (2) | C18—C17—C9 | 120.4 (2) |
O2—C7—C6 | 127.6 (2) | C22—C17—C9 | 120.90 (19) |
O2—C7—C8 | 121.32 (19) | C21—C22—C17 | 120.8 (2) |
C6—C7—C8 | 111.10 (18) | C21—C22—H22 | 119.6 |
O1—C8—C9 | 104.11 (15) | C17—C22—H22 | 119.6 |
O1—C8—C7 | 105.87 (16) | C20—C21—C22 | 119.8 (3) |
C9—C8—C7 | 112.77 (16) | C20—C21—H21 | 120.1 |
O1—C8—S1 | 108.32 (13) | C22—C21—H21 | 120.1 |
C9—C8—S1 | 117.48 (14) | C21—C20—C19 | 120.0 (2) |
C7—C8—S1 | 107.57 (14) | C21—C20—H20 | 120.0 |
C10—C9—C17 | 111.83 (16) | C19—C20—H20 | 120.0 |
C10—C9—C8 | 99.02 (16) | C20—C19—C18 | 120.5 (3) |
C17—C9—C8 | 114.22 (16) | C20—C19—H19 | 119.8 |
C10—C9—H9 | 110.4 | C18—C19—H19 | 119.8 |
C17—C9—H9 | 110.4 | C19—C18—C17 | 120.3 (3) |
C8—C9—H9 | 110.4 | C19—C18—H18 | 119.8 |
N1—C10—C11 | 120.21 (19) | C17—C18—H18 | 119.8 |
N1—C10—C9 | 113.72 (18) | C10—N1—O1 | 109.23 (16) |
C11—C10—C9 | 125.98 (19) | N1—O1—C8 | 107.90 (14) |
C16—C11—C12 | 118.5 (2) | C1—S1—C8 | 92.77 (10) |
C16—C11—C10 | 121.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···O2i | 0.93 | 2.62 | 3.462 (3) | 152 |
C9—H9···O1ii | 0.98 | 2.66 | 3.564 (2) | 154 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1/2, y−1/2, z. |
Acknowledgements
The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.
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