Methyl 2-(3-oxo-3,4-dihydro-2H-1,4-benzothia­zin-4-yl)acetate

Barryala, Y.; Massip, S.; Lazar, S.; Essassi, E.M.; Zouihri, H.

doi:10.1107/S1600536811006477

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o724

doi:10.1107/S1600536811006477

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Methyl 2-(3-oxo-3,4-dihydro-2H-1,4-benzothiazin-4-yl)acetate

Yamna Barryala,^a Stéphane Massip,^b Saïd Lazar,^c ^* El Mokhtar Essassi ^d and Hafid Zouihri ^e

^aLaboratoire de Chimie Organique et Etudes Physico-chimiques ENS Takaddoum, Rabat, Morocco, ^bLaboratoire de Chimie Physique et Minérale, Service de Cristallographie, Université Victor Ségalen Bordeaux 2, Bordeaux Cedex, France, ^cLaboratoire de Biochimie, Environnement et Agroalimentaire (URAC 36), Faculté des Sciences et Techniques Mohammedia, Université Hassan II Mohammedia–Casablana, BP 146, 20800 Mohammedia, Morocco, ^dLaboratoire de Chimie Organique Hétérocyclique, Faculté des Sciences de Rabat, Morocco, and ^eLaboratoires de Diffraction des Rayons X, Centre Nationale pour la Recherche Scientifique et Technique, Rabat, Morocco
^*Correspondence e-mail: lazar_said@yahoo.fr

(Received 11 February 2011; accepted 20 February 2011; online 26 February 2011)

In the crystal structure of the title compound, C₁₁H₁₁NO₃S, the molecules are linked by intermolecular C—H⋯O hydrogen-bond interactions. The heterocyclic thiazine ring adopts a conformation intermediate between twist and boat.

Related literature

For general background to the synthesis of benzothiazines, see: Harmata et al. (2005 ). For the pharmacological activity of benzothiazine derivatives, see: Lopatina et al. (1982 ). For related structures, see: Saeed et al. (2010 ); Aouine et al. (2010 ).

Experimental

Crystal data

C₁₁H₁₁NO₃S
M_r = 237.27
Monoclinic, P 2₁ /c
a = 17.347 (5) Å
b = 8.724 (2) Å
c = 7.274 (1) Å
β = 98.71 (2)°
V = 1088.1 (4) Å³
Z = 4
Cu Kα radiation
μ = 2.59 mm⁻¹
T = 296 K
0.20 × 0.15 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.625, T_max = 0.697
1852 measured reflections
1852 independent reflections
1654 reflections with I > 2σ(I)
2 standard reflections every 90 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.123
S = 1.03
1852 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O14	0.93	2.51	3.411 (3)	164

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811006477/bt5472sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811006477/bt5472Isup2.hkl

checkCIF report

Comment top

Several derivatives of benzothiazines, particularly those carrying a keto group on the thiazine part of the molecule, show stimulant and antidepressant activity. [Lopatina et al. 1982].

The goal of the present work was the synthesis, the crystal structure determination and the biological teste of the methyl (3-oxo-2,3-dihydro-4H-1,4-benzothiazin-4-yl)acetate. [Harmata et al. 2005].

In the crystal structure of the title compound (Fig. 1), the molecules exhibit C···H—O intermolecular H-bonds interactions (Fig. 2). The heterocyclic thiazine ring adopt half-chair conformation with the S and N atoms displaced by 0.357 (5) and 0.304 (15) Å, respectively, on the opposite sides from the mean plane formed by the remaining ring atoms. The methyl acetate group, which is almost planar with the r. m.s deviaton of 0.042 (14) Å, is iclined at dihedral angle of 88.31 (9)° and 74.67 (9)° with respect to the thiazine and benzene ring respectively.

The dihedral angle between the aromatic benzene ring C1–C6 and thiazine ring C5/C6/N7/C8/C9/S10 is 17.02 (9)° while the methyl acetate group C12/C13/O14/O15/C16 is oriented at dihedral angle of 81.30 (8)° with respect to the benzothiazine ring.

In the title compound (Fig. 1), the bond distances and angles agree with the cortresponding bond distances and angles reported in related compounds [Saeed et al. 2010 and Aouine et al. 2010].

Related literature top

For general background to the synthesis of benzothiazines, see: Harmata et al. (2005). For the pharmacological activity of benzothiazine derivatives, see: Lopatina et al. (1982). For related structures, see: Saeed et al. (2010); Aouine et al. (2010).

Experimental top

To 1,4-benzithiazin-3-one (0.25 g, 1.5 mmol), potassium carbonate (0.41 g, 3 mmol), in ketone (15 ml) was added methyl chloroacetate (0.32 g, 3 mmol). The mixture was heated to reflux for 48 h. The salts were removed by filtration and the filtrate concentrated under reduced pressure. The residue was separated by chromatography on a column of silica gel with dichloromethane/diethyl ether (9/1) as eluent. Crystals were isolated when the solvent was allowed to evaporate.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: CAD-4 Software (Enraf–Nonius, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular view of the title compound showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view showing the chain formed by C—H···O hydrogen bondings. H atoms not involved in hydrogen bonds have been omitted for clarity.

Methyl 2-(3-oxo-3,4-dihydro-2H-1,4-benzothiazin-4-yl)acetate top

Crystal data top

C₁₁H₁₁NO₃S	F(000) = 496
M_r = 237.27	D_x = 1.448 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 17.347 (5) Å	θ = 25.0–35.0°
b = 8.724 (2) Å	µ = 2.59 mm⁻¹
c = 7.274 (1) Å	T = 296 K
β = 98.71 (2)°	Prism, colourless
V = 1088.1 (4) Å³	0.20 × 0.15 × 0.15 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1654 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 64.9°, θ_min = 2.6°
ω–2θ scans	h = −20→20
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
T_min = 0.625, T_max = 0.697	l = 0→8
1852 measured reflections	2 standard reflections every 90 min
1852 independent reflections	intensity decay: none

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) = 0.123	w = 1/[σ²(F_o²) + (0.0891P)² + 0.2952P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
1852 reflections	Δρ_max = 0.31 e Å⁻³
147 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.025 (2)

Crystal data top

C₁₁H₁₁NO₃S	V = 1088.1 (4) Å³
M_r = 237.27	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 17.347 (5) Å	µ = 2.59 mm⁻¹
b = 8.724 (2) Å	T = 296 K
c = 7.274 (1) Å	0.20 × 0.15 × 0.15 mm
β = 98.71 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1654 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.625, T_max = 0.697	2 standard reflections every 90 min
1852 measured reflections	intensity decay: none
1852 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.03	Δρ_max = 0.31 e Å⁻³
1852 reflections	Δρ_min = −0.28 e Å⁻³
147 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	0.06412 (11)	1.0010 (2)	−0.1876 (3)	0.0408 (5)
C12	0.34845 (11)	0.9981 (2)	−0.1202 (3)	0.0425 (5)
C13	0.38184 (11)	1.1551 (2)	−0.0708 (3)	0.0385 (5)
C16	0.48971 (13)	1.3152 (3)	−0.0896 (3)	0.0523 (6)
C2	0.06020 (13)	1.0995 (2)	−0.3366 (3)	0.0462 (5)
C3	0.12837 (14)	1.1575 (2)	−0.3843 (3)	0.0477 (5)
C4	0.19978 (12)	1.1181 (2)	−0.2852 (3)	0.0411 (5)
C5	0.13542 (10)	0.9596 (2)	−0.0860 (2)	0.0342 (4)
C6	0.20474 (10)	1.0183 (2)	−0.1350 (2)	0.0325 (4)
C8	0.29001 (11)	0.9244 (2)	0.1449 (3)	0.0424 (5)
C9	0.22014 (12)	0.9212 (3)	0.2432 (3)	0.0480 (5)
H1	0.0183	0.9615	−0.1545	0.049*
H12A	0.3363	0.9889	−0.2544	0.051*
H12B	0.3870	0.9207	−0.0761	0.051*
H16A	0.4570	1.3905	−0.1589	0.078*
H16B	0.5394	1.3128	−0.1325	0.078*
H16C	0.4970	1.3413	0.0401	0.078*
H2	0.0122	1.1265	−0.4041	0.055*
H3	0.1262	1.2242	−0.4847	0.057*
H4	0.2451	1.1588	−0.3192	0.049*
H9A	0.2064	1.0251	0.2730	0.058*
H9B	0.2327	0.8649	0.3589	0.058*
N7	0.27801 (9)	0.97159 (18)	−0.0378 (2)	0.0371 (4)
O11	0.35438 (9)	0.8896 (2)	0.2240 (2)	0.0645 (5)
O14	0.34929 (8)	1.25486 (18)	−0.0003 (2)	0.0561 (5)
O15	0.45320 (8)	1.16608 (16)	−0.1160 (2)	0.0454 (4)
S10	0.13827 (3)	0.83215 (6)	0.10137 (7)	0.0470 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0361 (10)	0.0407 (10)	0.0462 (11)	−0.0021 (8)	0.0082 (8)	−0.0077 (8)
C2	0.0487 (11)	0.0415 (11)	0.0450 (11)	0.0044 (9)	−0.0043 (9)	−0.0055 (9)
C3	0.0651 (14)	0.0391 (11)	0.0370 (10)	−0.0035 (9)	0.0012 (9)	0.0033 (8)
C4	0.0502 (11)	0.0370 (10)	0.0385 (10)	−0.0082 (9)	0.0144 (8)	0.0011 (8)
C5	0.0378 (9)	0.0294 (9)	0.0373 (10)	−0.0026 (7)	0.0121 (7)	−0.0040 (7)
C6	0.0359 (9)	0.0287 (9)	0.0343 (9)	−0.0022 (7)	0.0098 (7)	−0.0042 (7)
N7	0.0312 (8)	0.0376 (8)	0.0447 (9)	−0.0005 (6)	0.0128 (6)	0.0019 (7)
C8	0.0408 (10)	0.0393 (10)	0.0471 (11)	0.0024 (8)	0.0071 (8)	0.0026 (8)
C9	0.0509 (11)	0.0567 (13)	0.0379 (10)	0.0024 (10)	0.0116 (9)	0.0121 (9)
S10	0.0442 (4)	0.0470 (4)	0.0529 (4)	−0.0048 (2)	0.0170 (2)	0.0152 (2)
O11	0.0449 (9)	0.0783 (12)	0.0667 (11)	0.0108 (8)	−0.0030 (7)	0.0096 (9)
C12	0.0334 (9)	0.0418 (11)	0.0560 (12)	0.0009 (8)	0.0185 (8)	−0.0028 (9)
C13	0.0295 (9)	0.0454 (11)	0.0419 (10)	−0.0017 (8)	0.0098 (7)	−0.0010 (8)
O14	0.0455 (9)	0.0543 (10)	0.0735 (11)	−0.0063 (7)	0.0257 (8)	−0.0220 (8)
O15	0.0317 (7)	0.0491 (8)	0.0579 (9)	−0.0035 (5)	0.0147 (6)	0.0000 (6)
C16	0.0405 (11)	0.0562 (13)	0.0605 (13)	−0.0111 (9)	0.0085 (10)	0.0037 (11)

Geometric parameters (Å, º) top

S10—C5	1.7538 (17)	C5—C6	1.402 (2)
S10—C9	1.800 (2)	C8—C9	1.498 (3)
O11—C8	1.215 (3)	C12—C13	1.509 (3)
O14—C13	1.195 (2)	C1—H1	0.9300
O15—C13	1.332 (2)	C2—H2	0.9300
O15—C16	1.447 (3)	C3—H3	0.9300
N7—C6	1.418 (2)	C4—H4	0.9300
N7—C8	1.377 (3)	C9—H9A	0.9700
N7—C12	1.459 (3)	C9—H9B	0.9700
C1—C2	1.377 (3)	C12—H12A	0.9700
C1—C5	1.389 (3)	C12—H12B	0.9700
C2—C3	1.378 (3)	C16—H16A	0.9600
C3—C4	1.379 (3)	C16—H16B	0.9600
C4—C6	1.390 (3)	C16—H16C	0.9600

C5—S10—C9	95.67 (10)	C5—C1—H1	120.00
C13—O15—C16	115.88 (16)	C1—C2—H2	120.00
C6—N7—C8	124.10 (15)	C3—C2—H2	121.00
C6—N7—C12	119.55 (15)	C2—C3—H3	120.00
C8—N7—C12	115.50 (16)	C4—C3—H3	120.00
C2—C1—C5	121.00 (18)	C3—C4—H4	120.00
C1—C2—C3	119.0 (2)	C6—C4—H4	120.00
C2—C3—C4	120.93 (19)	S10—C9—H9A	109.00
C3—C4—C6	120.73 (19)	S10—C9—H9B	109.00
S10—C5—C1	119.76 (14)	C8—C9—H9A	109.00
S10—C5—C6	120.32 (13)	C8—C9—H9B	109.00
C1—C5—C6	119.92 (15)	H9A—C9—H9B	108.00
N7—C6—C4	121.09 (16)	N7—C12—H12A	109.00
N7—C6—C5	120.47 (14)	N7—C12—H12B	109.00
C4—C6—C5	118.39 (16)	C13—C12—H12A	109.00
O11—C8—N7	121.72 (18)	C13—C12—H12B	109.00
O11—C8—C9	121.43 (19)	H12A—C12—H12B	108.00
N7—C8—C9	116.83 (17)	O15—C16—H16A	109.00
S10—C9—C8	111.08 (15)	O15—C16—H16B	109.00
N7—C12—C13	111.18 (16)	O15—C16—H16C	109.00
O14—C13—O15	124.83 (17)	H16A—C16—H16B	109.00
O14—C13—C12	125.04 (18)	H16A—C16—H16C	109.00
O15—C13—C12	110.13 (16)	H16B—C16—H16C	109.00
C2—C1—H1	119.00

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O14	0.93	2.51	3.411 (3)	164

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁NO₃S
M_r	237.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	17.347 (5), 8.724 (2), 7.274 (1)
β (°)	98.71 (2)
V (Å³)	1088.1 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.59
Crystal size (mm)	0.20 × 0.15 × 0.15

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.625, 0.697
No. of measured, independent and observed [I > 2σ(I)] reflections	1852, 1852, 1654
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.587

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.123, 1.03
No. of reflections	1852
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.28

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O14	0.93	2.51	3.411 (3)	164

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o724

doi:10.1107/S1600536811006477

Open

access