organic compounds
(Z)-4-n-Butyl-2-(4-chlorobenzylidene)-2H-1,4-benzothiazin-3(4H)-one
aLaboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétence Pharmacochimie, Av. Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, bLaboratoire de Chimie Organique Appliquée, Faculté des Sciences et, Techniques, Université Sidi Mohammed Ben Abdellah, Fès, Morocco, and cDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA
*Correspondence e-mail: nadouchsebbarkheira@gmail.com
In the title compound, C19H18ClNOS, the thiazin-3-one ring adopts a slightly distorted screw-boat conformation. An intramolecular C—H⋯S hydrogen bond encloses an S(6) ring and affects the overall conformation of the molecule. The dihedral angle between the two phenyl rings is 52.3 (2)°. In the crystal, weak C—H⋯O intermolecular interactions stabilize the crystal packing.
Keywords: crystal structure; benzothiazine; hydrogen bonds.
CCDC reference: 1555441
Structure description
1,4-Benzothiazine-containing compounds are important due to their potential applications in the treatment of diabetes complications, by inhibiting aldose reductase (Aotsuka et al., 1994). They are also used as analgesics (Wammack et al., 2002), Ca2+ antagonists (Fujimura et al., 1996), and have antimicrobial properties (Zia-ur-Rehman et al., 2009). As a continuation of our previous work on the synthesis of new 1,4-benzothiazine derivatives (Sebbar et al.,2016a,b; Ellouz et al.,2017a,b), we report here the synthesis and of the title compound (Fig. 1). This was prepared by reacting (Z)-2-(4-chlorobenzylidene)-2H-1,4-benzothiazin-3(4H)-one with 1-bromobutane, under conditions using tetra-n-butyl ammonium bromide (TBAB) as a catalyst and potassium carbonate as the base.
The title compound crystallizes with one independent molecule in the ). The thiazine-3-one ring of the [1,4]thiazin-3-one moiety adopts a slightly distorted screw-boat conformation [puckering parameters: Q = 0.468 (7) Å, θ = 69.8 (7)° and φ = 25.949 (3)°]. An intramolecular C15—H15⋯S1 hydrogen bond forms an S(6) ring motif, and at least partially determines the conformation of the molecule. The dihedral angle between the phenyl rings is 52.3 (2)°.
(Fig. 1In the crystal, weak C—H⋯O hydrogen bonds involving O1 as the acceptor, Table 1, link the molecules into a two-dimensional network (Fig. 2).
Synthesis and crystallization
To a solution of (Z)-2-(4-chlorobenzylidene)-2H-1,4-benzothiazin-3(4H)-one (0.49 g,1.5mmol), potassium carbonate (0.41 g,3 mmol) and tetra-n-butyl ammonium bromide (0.048 g,0.15 mmol) in DMF (18 ml) was added 1-bromobutane (3 mmol). Stirring was continued at room temperature for 24 h. The mixture was filtered and the solvent removed. The residue was then washed with water. The organic compound obtained was chromatographed on a column of silica gel with ethyl acetate–hexane (9/1) as the Colorless prismatic crystals were isolated when the solvent was allowed to evaporate (yield = 51%).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1555441
https://doi.org/10.1107/S2414314617008707/sj4118sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617008707/sj4118Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617008707/sj4118Isup3.cdx
Supporting information file. DOI: https://doi.org/10.1107/S2414314617008707/sj4118Isup4.cml
Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell
CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C19H18ClNOS | Z = 2 |
Mr = 343.85 | F(000) = 360 |
Triclinic, P1 | Dx = 1.316 Mg m−3 |
a = 8.8898 (8) Å | Cu Kα radiation, λ = 1.54184 Å |
b = 8.9885 (9) Å | Cell parameters from 2206 reflections |
c = 12.1973 (10) Å | θ = 5.5–70.9° |
α = 89.908 (8)° | µ = 3.09 mm−1 |
β = 84.490 (7)° | T = 293 K |
γ = 63.534 (9)° | Prism, colourless |
V = 867.53 (15) Å3 | 0.34 × 0.32 × 0.14 mm |
Rigaku Oxford Diffraction diffractometer | 3279 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source | 2807 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 16.0416 pixels mm-1 | θmax = 71.5°, θmin = 3.6° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015) | k = −11→10 |
Tmin = 0.382, Tmax = 1.000 | l = −14→14 |
5496 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.049 | w = 1/[σ2(Fo2) + (0.0787P)2 + 0.2112P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.146 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.30 e Å−3 |
3279 reflections | Δρmin = −0.32 e Å−3 |
210 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0051 (9) |
Primary atom site location: dual |
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 | ||
Cl1 | 0.09239 (15) | 1.18172 (14) | −0.02253 (9) | 0.1305 (5) | |
S1 | 0.73755 (8) | 0.52007 (7) | 0.23423 (4) | 0.0561 (2) | |
O1 | 0.7170 (2) | 0.7404 (2) | 0.50943 (14) | 0.0629 (5) | |
N1 | 0.7797 (2) | 0.4711 (2) | 0.47968 (14) | 0.0461 (4) | |
C1 | 0.7158 (3) | 0.6329 (3) | 0.44911 (17) | 0.0467 (5) | |
C2 | 0.6464 (3) | 0.6753 (3) | 0.34053 (17) | 0.0447 (4) | |
C3 | 0.7545 (3) | 0.3470 (3) | 0.30826 (19) | 0.0502 (5) | |
C4 | 0.7543 (3) | 0.2137 (3) | 0.2500 (2) | 0.0667 (7) | |
H4 | 0.7439 | 0.2195 | 0.1747 | 0.080* | |
C5 | 0.7696 (4) | 0.0737 (4) | 0.3035 (3) | 0.0785 (8) | |
H5 | 0.7724 | −0.0163 | 0.2643 | 0.094* | |
C6 | 0.7806 (4) | 0.0673 (3) | 0.4149 (3) | 0.0784 (8) | |
H6 | 0.7886 | −0.0266 | 0.4513 | 0.094* | |
C7 | 0.7800 (3) | 0.1990 (3) | 0.4738 (2) | 0.0644 (6) | |
H7 | 0.7868 | 0.1934 | 0.5494 | 0.077* | |
C8 | 0.7693 (3) | 0.3403 (3) | 0.42042 (18) | 0.0470 (5) | |
C9 | 0.5312 (3) | 0.8316 (3) | 0.32848 (17) | 0.0487 (5) | |
H9 | 0.5091 | 0.9029 | 0.3895 | 0.058* | |
C10 | 0.4338 (3) | 0.9109 (3) | 0.23699 (18) | 0.0505 (5) | |
C11 | 0.2955 (4) | 1.0643 (3) | 0.2594 (2) | 0.0692 (7) | |
H11 | 0.2722 | 1.1131 | 0.3301 | 0.083* | |
C12 | 0.1918 (4) | 1.1465 (4) | 0.1810 (3) | 0.0783 (8) | |
H12 | 0.0998 | 1.2496 | 0.1985 | 0.094* | |
C13 | 0.2237 (4) | 1.0772 (4) | 0.0775 (3) | 0.0783 (8) | |
C14 | 0.3614 (6) | 0.9286 (4) | 0.0506 (3) | 0.1164 (16) | |
H14 | 0.3849 | 0.8826 | −0.0209 | 0.140* | |
C15 | 0.4653 (5) | 0.8471 (4) | 0.1298 (2) | 0.0944 (12) | |
H15 | 0.5595 | 0.7462 | 0.1106 | 0.113* | |
C16 | 0.8499 (3) | 0.4380 (3) | 0.58673 (17) | 0.0513 (5) | |
H16A | 0.9118 | 0.5024 | 0.5944 | 0.062* | |
H16B | 0.9298 | 0.3213 | 0.5868 | 0.062* | |
C17 | 0.7187 (3) | 0.4791 (3) | 0.68574 (19) | 0.0560 (6) | |
H17A | 0.6484 | 0.4242 | 0.6754 | 0.067* | |
H17B | 0.6467 | 0.5981 | 0.6918 | 0.067* | |
C18 | 0.8018 (4) | 0.4236 (4) | 0.7914 (2) | 0.0733 (8) | |
H18A | 0.8518 | 0.3032 | 0.7922 | 0.088* | |
H18B | 0.8921 | 0.4561 | 0.7923 | 0.088* | |
C19 | 0.6794 (5) | 0.4967 (5) | 0.8941 (2) | 0.1002 (12) | |
H19A | 0.5910 | 0.4630 | 0.8945 | 0.150* | |
H19B | 0.6314 | 0.6159 | 0.8947 | 0.150* | |
H19C | 0.7382 | 0.4577 | 0.9582 | 0.150* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.1339 (9) | 0.1157 (8) | 0.0988 (7) | −0.0060 (6) | −0.0706 (7) | 0.0190 (6) |
S1 | 0.0688 (4) | 0.0496 (3) | 0.0409 (3) | −0.0181 (3) | −0.0068 (2) | 0.0018 (2) |
O1 | 0.0915 (12) | 0.0568 (10) | 0.0514 (9) | −0.0403 (9) | −0.0224 (8) | 0.0055 (7) |
N1 | 0.0508 (9) | 0.0494 (10) | 0.0414 (9) | −0.0247 (8) | −0.0084 (7) | 0.0074 (7) |
C1 | 0.0537 (11) | 0.0504 (11) | 0.0423 (10) | −0.0286 (9) | −0.0069 (8) | 0.0036 (9) |
C2 | 0.0519 (11) | 0.0448 (11) | 0.0418 (10) | −0.0253 (9) | −0.0057 (8) | 0.0028 (8) |
C3 | 0.0483 (11) | 0.0447 (11) | 0.0558 (12) | −0.0189 (9) | −0.0062 (9) | 0.0007 (9) |
C4 | 0.0734 (16) | 0.0558 (14) | 0.0703 (16) | −0.0281 (12) | −0.0084 (13) | −0.0105 (12) |
C5 | 0.089 (2) | 0.0566 (15) | 0.094 (2) | −0.0385 (14) | 0.0012 (16) | −0.0144 (15) |
C6 | 0.0883 (19) | 0.0477 (14) | 0.101 (2) | −0.0353 (13) | 0.0089 (16) | 0.0044 (14) |
C7 | 0.0722 (15) | 0.0531 (13) | 0.0659 (15) | −0.0282 (12) | 0.0025 (12) | 0.0074 (11) |
C8 | 0.0428 (10) | 0.0425 (11) | 0.0544 (12) | −0.0185 (8) | −0.0017 (8) | 0.0026 (9) |
C9 | 0.0598 (12) | 0.0453 (11) | 0.0436 (11) | −0.0254 (9) | −0.0068 (9) | 0.0006 (8) |
C10 | 0.0579 (12) | 0.0445 (11) | 0.0482 (11) | −0.0215 (9) | −0.0089 (9) | 0.0025 (9) |
C11 | 0.0773 (16) | 0.0573 (14) | 0.0561 (14) | −0.0139 (12) | −0.0132 (12) | −0.0074 (11) |
C12 | 0.0662 (16) | 0.0634 (16) | 0.0769 (18) | −0.0019 (13) | −0.0160 (14) | 0.0033 (14) |
C13 | 0.0865 (19) | 0.0689 (17) | 0.0680 (17) | −0.0186 (14) | −0.0388 (15) | 0.0127 (13) |
C14 | 0.154 (3) | 0.073 (2) | 0.0598 (18) | 0.011 (2) | −0.045 (2) | −0.0094 (15) |
C15 | 0.116 (2) | 0.0600 (16) | 0.0530 (15) | 0.0116 (16) | −0.0220 (16) | −0.0036 (12) |
C16 | 0.0461 (11) | 0.0623 (13) | 0.0461 (11) | −0.0237 (10) | −0.0110 (9) | 0.0111 (9) |
C17 | 0.0521 (12) | 0.0673 (14) | 0.0468 (12) | −0.0246 (10) | −0.0075 (9) | 0.0119 (10) |
C18 | 0.0680 (15) | 0.096 (2) | 0.0485 (13) | −0.0281 (14) | −0.0131 (11) | 0.0150 (13) |
C19 | 0.098 (2) | 0.141 (3) | 0.0465 (15) | −0.040 (2) | −0.0061 (15) | 0.0107 (17) |
Cl1—C13 | 1.740 (3) | C10—C15 | 1.380 (4) |
S1—C2 | 1.756 (2) | C11—H11 | 0.9300 |
S1—C3 | 1.753 (2) | C11—C12 | 1.368 (4) |
O1—C1 | 1.220 (3) | C12—H12 | 0.9300 |
N1—C1 | 1.371 (3) | C12—C13 | 1.355 (4) |
N1—C8 | 1.424 (3) | C13—C14 | 1.363 (4) |
N1—C16 | 1.474 (3) | C14—H14 | 0.9300 |
C1—C2 | 1.492 (3) | C14—C15 | 1.374 (4) |
C2—C9 | 1.337 (3) | C15—H15 | 0.9300 |
C3—C4 | 1.395 (3) | C16—H16A | 0.9700 |
C3—C8 | 1.386 (3) | C16—H16B | 0.9700 |
C4—H4 | 0.9300 | C16—C17 | 1.517 (3) |
C4—C5 | 1.375 (4) | C17—H17A | 0.9700 |
C5—H5 | 0.9300 | C17—H17B | 0.9700 |
C5—C6 | 1.371 (5) | C17—C18 | 1.519 (3) |
C6—H6 | 0.9300 | C18—H18A | 0.9700 |
C6—C7 | 1.384 (4) | C18—H18B | 0.9700 |
C7—H7 | 0.9300 | C18—C19 | 1.512 (4) |
C7—C8 | 1.395 (3) | C19—H19A | 0.9600 |
C9—H9 | 0.9300 | C19—H19B | 0.9600 |
C9—C10 | 1.462 (3) | C19—H19C | 0.9600 |
C10—C11 | 1.383 (3) | ||
C3—S1—C2 | 99.73 (10) | C11—C12—H12 | 120.1 |
C1—N1—C8 | 124.60 (18) | C13—C12—C11 | 119.8 (3) |
C1—N1—C16 | 115.97 (17) | C13—C12—H12 | 120.1 |
C8—N1—C16 | 119.20 (17) | C12—C13—Cl1 | 119.9 (2) |
O1—C1—N1 | 120.5 (2) | C12—C13—C14 | 120.3 (3) |
O1—C1—C2 | 120.45 (19) | C14—C13—Cl1 | 119.9 (2) |
N1—C1—C2 | 119.09 (18) | C13—C14—H14 | 120.2 |
C1—C2—S1 | 116.82 (15) | C13—C14—C15 | 119.6 (3) |
C9—C2—S1 | 124.85 (17) | C15—C14—H14 | 120.2 |
C9—C2—C1 | 118.04 (19) | C10—C15—H15 | 119.1 |
C4—C3—S1 | 117.58 (19) | C14—C15—C10 | 121.9 (3) |
C8—C3—S1 | 121.84 (17) | C14—C15—H15 | 119.1 |
C8—C3—C4 | 120.6 (2) | N1—C16—H16A | 108.7 |
C3—C4—H4 | 119.9 | N1—C16—H16B | 108.7 |
C5—C4—C3 | 120.1 (3) | N1—C16—C17 | 114.37 (17) |
C5—C4—H4 | 119.9 | H16A—C16—H16B | 107.6 |
C4—C5—H5 | 120.1 | C17—C16—H16A | 108.7 |
C6—C5—C4 | 119.8 (3) | C17—C16—H16B | 108.7 |
C6—C5—H5 | 120.1 | C16—C17—H17A | 109.4 |
C5—C6—H6 | 119.7 | C16—C17—H17B | 109.4 |
C5—C6—C7 | 120.7 (3) | C16—C17—C18 | 111.19 (19) |
C7—C6—H6 | 119.7 | H17A—C17—H17B | 108.0 |
C6—C7—H7 | 119.8 | C18—C17—H17A | 109.4 |
C6—C7—C8 | 120.4 (3) | C18—C17—H17B | 109.4 |
C8—C7—H7 | 119.8 | C17—C18—H18A | 109.0 |
C3—C8—N1 | 121.16 (19) | C17—C18—H18B | 109.0 |
C3—C8—C7 | 118.4 (2) | H18A—C18—H18B | 107.8 |
C7—C8—N1 | 120.4 (2) | C19—C18—C17 | 112.9 (2) |
C2—C9—H9 | 114.1 | C19—C18—H18A | 109.0 |
C2—C9—C10 | 131.8 (2) | C19—C18—H18B | 109.0 |
C10—C9—H9 | 114.1 | C18—C19—H19A | 109.5 |
C11—C10—C9 | 117.3 (2) | C18—C19—H19B | 109.5 |
C15—C10—C9 | 126.4 (2) | C18—C19—H19C | 109.5 |
C15—C10—C11 | 116.4 (2) | H19A—C19—H19B | 109.5 |
C10—C11—H11 | 119.0 | H19A—C19—H19C | 109.5 |
C12—C11—C10 | 122.1 (2) | H19B—C19—H19C | 109.5 |
C12—C11—H11 | 119.0 |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O1i | 0.93 | 2.53 | 3.410 (3) | 158 |
C11—H11···O1ii | 0.93 | 2.39 | 3.290 (3) | 162 |
C15—H15···S1 | 0.93 | 2.55 | 3.219 (3) | 129 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+2, −z+1. |
Acknowledgements
JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.
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