4-Methyl-3,4-di­hydro-2H-1,4-benzo­thia­zin-3-one

Ellouz, M.; Sebbar, N.K.; Ouzidan, Y.; Essassi, E.M.; Mague, J.T.

doi:10.1107/S2414314617000979

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 2| February 2017| x170097

https://doi.org/10.1107/S2414314617000979

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4-Methyl-3,4-dihydro-2H-1,4-benzothiazin-3-one

Mohamed Ellouz,^a Nada Kheira Sebbar,^a ^* Younes Ouzidan,^b El Mokhtar Essassi ^a and Joel T. Mague ^c

^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, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route d'Imouzzer, BP 2202, Fez, Morocco, and ^cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: nadouchsebbarkheira@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 11 January 2017; accepted 18 January 2017; online 3 February 2017)

In the crystal of the title compound, C₉H₉NOS, the molecules are linked by C—H⋯O hydrogen bonds to generate bilayers lying parallel to (001).

Keywords: crystal structure; bilayer; hydrogen bond; benzothiazine.

CCDC reference: 1528393

Structure description

As a continuation of our studies of N-substituted benzothiazines (Sebbar et al., 2014 , 2016 ; Ellouz et al., 2015 ), we now describe the synthesis and structure of the title compound, (Fig. 1).

Figure 1
The title molecule with 50% probability ellipsoids.

A puckering analysis of the heterocyclic ring gave the parameters Q = 0.668 (1) Å, θ = 113.2 (1)° and φ = 146.9°: atoms C1, C6, S1 and N1 are roughly coplanar (r.m.s. deviation = 0.046 Å) and atoms C7 and C8 deviate in the same sense [by 0.476 (1) and 1.111 (1) Å, respectively] from the mean plane. In the crystal, the molecules are linked by C—H⋯O hydrogen bonds (Table 1) to form bilayers oriented parallel to (001) (Figs. 2 and 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯O1ⁱ	0.983 (18)	2.301 (18)	3.2819 (16)	175.0 (15)
C9—H9B⋯O1ⁱⁱ	0.998 (19)	2.62 (2)	3.6157 (17)	173.3 (15)
C9—H9C⋯O1ⁱⁱⁱ	0.995 (17)	2.512 (17)	3.4265 (16)	152.6 (14)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Figure 2
Detail of the intermolecular C—H⋯O hydrogen bonding [symmetry codes: (i) $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, 1 − z; (ii) $[{1\over 2}]$ − x, $[{1\over 2}]$ + y, z; (iii) − $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, 1 − z].

Figure 3
Packing viewed along the a axis with C—H⋯O hydrogen bonds shown as dotted lines.

Synthesis and crystallization

To a solution of 3,4-dihydro-2H-1,4-benzothiazin-3-one (2 mmol), potassium carbonate (4 mmol) and tetra n-butyl ammonium bromide (0.2 mmol) in DMF (15 ml) was added iodomethane (4 mmol). Stirring was continued at room temperature for 12 h. The mixture was filtered and the solvent removed. The residue was extracted with water. The organic compound was chromatographed on a column of silica gel with ethyl acetate–hexane (9:1) as eluent. Brown crystals of the title compound were isolated when the solvent was allowed to evaporate (yield 57%; m.p. 370 K).

Refinement

Crystal and refinement data are presented in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₉NOS
M_r	179.23
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	150
a, b, c (Å)	7.3148 (6), 8.4030 (6), 27.670 (2)
V (Å³)	1700.8 (2)
Z	8
Radiation type	Cu Kα
μ (mm⁻¹)	2.95
Crystal size (mm)	0.33 × 0.31 × 0.04

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.63, 0.88
No. of measured, independent and observed [I > 2σ(I)] reflections	16139, 1674, 1628
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.076, 1.04
No. of reflections	1674
No. of parameters	146
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.24
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1528393

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617000979/hb4112sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617000979/hb4112Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617000979/hb4112Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617000979/hb4112Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

4-Methyl-3,4-dihydro-2H-1,4-benzothiazin-3-one top

Crystal data top

C₉H₉NOS	D_x = 1.400 Mg m⁻³
M_r = 179.23	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pbca	Cell parameters from 9930 reflections
a = 7.3148 (6) Å	θ = 3.2–72.4°
b = 8.4030 (6) Å	µ = 2.95 mm⁻¹
c = 27.670 (2) Å	T = 150 K
V = 1700.8 (2) Å³	Plate, colourless
Z = 8	0.33 × 0.31 × 0.04 mm
F(000) = 752

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	1674 independent reflections
Radiation source: INCOATEC IµS micro-focus source	1628 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.040
Detector resolution: 10.4167 pixels mm^-1	θ_max = 72.2°, θ_min = 3.2°
ω scans	h = −8→9
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −10→10
T_min = 0.63, T_max = 0.88	l = −34→30
16139 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.029	All H-atom parameters refined
wR(F²) = 0.076	w = 1/[σ²(F_o²) + (0.0383P)² + 0.7672P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.002
1674 reflections	Δρ_max = 0.29 e Å⁻³
146 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0029 (3)

Special details top

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.

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 > 2sigma(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
S1	0.70736 (4)	0.30751 (4)	0.62414 (2)	0.02827 (15)
O1	0.44820 (14)	0.32356 (11)	0.50834 (3)	0.0293 (2)
N1	0.36431 (14)	0.44168 (12)	0.57877 (3)	0.0207 (2)
C1	0.55962 (17)	0.44702 (14)	0.65097 (4)	0.0227 (3)
C2	0.59106 (19)	0.50090 (17)	0.69783 (5)	0.0302 (3)
H2	0.693 (2)	0.458 (2)	0.7141 (6)	0.039 (5)*
C3	0.4778 (2)	0.61424 (18)	0.71846 (5)	0.0347 (3)
H3	0.499 (3)	0.652 (2)	0.7512 (7)	0.046 (5)*
C4	0.3350 (2)	0.67709 (18)	0.69178 (5)	0.0320 (3)
H4	0.261 (3)	0.759 (2)	0.7048 (6)	0.047 (5)*
C5	0.29965 (17)	0.62271 (16)	0.64548 (5)	0.0257 (3)
H5	0.195 (2)	0.666 (2)	0.6276 (5)	0.030 (4)*
C6	0.40958 (16)	0.50524 (14)	0.62472 (4)	0.0200 (3)
C7	0.49111 (17)	0.38099 (14)	0.54745 (4)	0.0220 (3)
C8	0.68710 (17)	0.38743 (16)	0.56376 (5)	0.0254 (3)
H8A	0.731 (2)	0.492 (2)	0.5634 (6)	0.033 (4)*
H8B	0.759 (3)	0.319 (2)	0.5421 (6)	0.034 (4)*
C9	0.17297 (18)	0.44689 (17)	0.56278 (5)	0.0280 (3)
H9A	0.095 (2)	0.435 (2)	0.5922 (6)	0.034 (4)*
H9B	0.148 (3)	0.549 (2)	0.5456 (6)	0.043 (5)*
H9C	0.152 (2)	0.359 (2)	0.5394 (6)	0.033 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0234 (2)	0.0272 (2)	0.0342 (2)	0.00595 (11)	−0.00356 (11)	0.00232 (12)
O1	0.0317 (5)	0.0301 (5)	0.0261 (5)	−0.0038 (4)	−0.0010 (4)	−0.0083 (4)
N1	0.0175 (5)	0.0229 (5)	0.0217 (5)	0.0001 (4)	−0.0023 (4)	−0.0015 (4)
C1	0.0213 (6)	0.0234 (6)	0.0233 (6)	−0.0027 (5)	−0.0004 (4)	0.0032 (5)
C2	0.0280 (7)	0.0383 (7)	0.0242 (6)	−0.0054 (6)	−0.0050 (5)	0.0052 (5)
C3	0.0367 (8)	0.0469 (8)	0.0206 (6)	−0.0080 (6)	0.0020 (5)	−0.0050 (6)
C4	0.0322 (7)	0.0364 (7)	0.0275 (7)	−0.0012 (6)	0.0074 (6)	−0.0069 (5)
C5	0.0239 (6)	0.0270 (6)	0.0262 (6)	0.0010 (5)	0.0023 (5)	−0.0006 (5)
C6	0.0194 (6)	0.0214 (6)	0.0192 (6)	−0.0030 (4)	0.0008 (4)	0.0011 (4)
C7	0.0242 (6)	0.0189 (5)	0.0229 (6)	−0.0016 (5)	0.0007 (5)	−0.0012 (4)
C8	0.0209 (6)	0.0269 (6)	0.0283 (6)	0.0000 (5)	0.0018 (5)	−0.0044 (5)
C9	0.0202 (6)	0.0345 (7)	0.0294 (7)	0.0014 (5)	−0.0059 (5)	−0.0028 (6)

Geometric parameters (Å, º) top

S1—C1	1.7589 (13)	C3—H3	0.97 (2)
S1—C8	1.8067 (14)	C4—C5	1.3846 (19)
O1—C7	1.2257 (15)	C4—H4	0.94 (2)
N1—C7	1.3680 (16)	C5—C6	1.3967 (17)
N1—C6	1.4183 (15)	C5—H5	0.979 (17)
N1—C9	1.4684 (16)	C7—C8	1.5040 (18)
C1—C2	1.3924 (18)	C8—H8A	0.937 (19)
C1—C6	1.4042 (17)	C8—H8B	0.983 (18)
C2—C3	1.385 (2)	C9—H9A	0.998 (17)
C2—H2	0.943 (18)	C9—H9B	0.998 (19)
C3—C4	1.384 (2)	C9—H9C	0.995 (17)

C1—S1—C8	95.30 (6)	C5—C6—C1	118.91 (11)
C7—N1—C6	123.36 (10)	C5—C6—N1	120.02 (11)
C7—N1—C9	117.81 (10)	C1—C6—N1	121.00 (11)
C6—N1—C9	118.77 (10)	O1—C7—N1	122.17 (12)
C2—C1—C6	119.84 (12)	O1—C7—C8	121.54 (11)
C2—C1—S1	120.56 (10)	N1—C7—C8	116.29 (10)
C6—C1—S1	119.61 (9)	C7—C8—S1	110.02 (9)
C3—C2—C1	120.56 (13)	C7—C8—H8A	110.9 (10)
C3—C2—H2	122.5 (11)	S1—C8—H8A	109.3 (10)
C1—C2—H2	116.9 (11)	C7—C8—H8B	108.0 (11)
C4—C3—C2	119.59 (13)	S1—C8—H8B	107.6 (10)
C4—C3—H3	119.6 (12)	H8A—C8—H8B	110.9 (14)
C2—C3—H3	120.8 (12)	N1—C9—H9A	107.2 (10)
C3—C4—C5	120.59 (13)	N1—C9—H9B	110.2 (11)
C3—C4—H4	120.4 (12)	H9A—C9—H9B	111.7 (14)
C5—C4—H4	119.0 (12)	N1—C9—H9C	108.8 (10)
C4—C5—C6	120.40 (12)	H9A—C9—H9C	111.4 (14)
C4—C5—H5	119.5 (9)	H9B—C9—H9C	107.6 (13)
C6—C5—H5	120.1 (9)

C8—S1—C1—C2	−145.51 (11)	S1—C1—C6—N1	6.45 (16)
C8—S1—C1—C6	34.01 (11)	C7—N1—C6—C5	152.11 (12)
C6—C1—C2—C3	−1.42 (19)	C9—N1—C6—C5	−25.19 (16)
S1—C1—C2—C3	178.10 (11)	C7—N1—C6—C1	−30.72 (17)
C1—C2—C3—C4	−1.6 (2)	C9—N1—C6—C1	151.98 (12)
C2—C3—C4—C5	2.8 (2)	C6—N1—C7—O1	178.39 (11)
C3—C4—C5—C6	−1.0 (2)	C9—N1—C7—O1	−4.28 (17)
C4—C5—C6—C1	−1.97 (19)	C6—N1—C7—C8	−1.19 (16)
C4—C5—C6—N1	175.26 (11)	C9—N1—C7—C8	176.13 (11)
C2—C1—C6—C5	3.18 (18)	O1—C7—C8—S1	−129.74 (11)
S1—C1—C6—C5	−176.35 (9)	N1—C7—C8—S1	49.85 (13)
C2—C1—C6—N1	−174.02 (11)	C1—S1—C8—C7	−60.08 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O1ⁱ	0.983 (18)	2.301 (18)	3.2819 (16)	175.0 (15)
C9—H9B···O1ⁱⁱ	0.998 (19)	2.62 (2)	3.6157 (17)	173.3 (15)
C9—H9C···O1ⁱⁱⁱ	0.995 (17)	2.512 (17)	3.4265 (16)	152.6 (14)

Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) −x+1/2, y+1/2, z; (iii) x−1/2, −y+1/2, −z+1.

Acknowledgements

The support of NSF-MRI Grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

References

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