Crystal structure of 4-benzyl-2H-benzo[b][1,4]thia­zin-3(4H)-one

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

doi:10.1107/S2056989015022276

organic compounds

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Volume 71| Part 12| December 2015| Page o999

https://doi.org/10.1107/S2056989015022276

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Crystal structure of 4-benzyl-2H-benzo[b][1,4]thiazin-3(4H)-one

N. K. Sebbar,^a M. Ellouz,^a E. M. Essassi,^a Y. Ouzidan ^b ‡ and J. 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'immouzzer, BP 2202, Fez, Morocco, and ^cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: joelt@tulane.edu

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 18 November 2015; accepted 20 November 2015; online 28 November 2015)

In the title compound, C₁₅H₁₃NOS, the thiazine ring adopts a twisted boat conformation and the dihedral angle between the aromatic rings is 86.54 (4)°. In the crystal, molecules are linked by weak C—H⋯O interactions, resulting in chains along [010].

Keywords: crystal structure; 1,4-benzothiazine derivatives; C—H⋯O interactions.

CCDC reference: 1438105

1. Related literature

For related structures and background to 1,4-benzothiazine derivatives, see: Zerzouf et al. (2001 ); Sebbar et al. (2015 ).

2. Experimental

2.1. Crystal data

C₁₅H₁₃NOS
M_r = 255.32
Monoclinic, P 2₁ /c
a = 10.8711 (7) Å
b = 5.3815 (3) Å
c = 21.1997 (13) Å
β = 93.128 (1)°
V = 1238.39 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 150 K
0.31 × 0.19 × 0.15 mm

2.2. Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2015 ) T_min = 0.88, T_max = 0.96
22588 measured reflections
3318 independent reflections
2731 reflections with I > 2σ(I)
R_int = 0.034

2.3. Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.107
S = 1.06
3318 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯O1ⁱ	0.99	2.55	3.2504 (14)	128
C7—H7B⋯O1ⁱⁱ	0.99	2.53	3.4403 (15)	152
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y+1, z.

Data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT; 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, 2015b).

Supporting information

CCDC reference: 1438105

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989015022276/hb7545sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015022276/hb7545Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015022276/hb7545Isup3.cml

checkCIF report

Comment top

As a continuation of our research devoted to the development of substituted 1,4-benzothiazine derivatives (Zerzouf et al., 2001; Sebbar et al., 2015), we report the synthesis of a 1,4-benzothiazine derivative by reaction of benzyl chloride with 2H-benzo[b][1,4]thiazin-3(4H)-one in the presence of tetra-n-butylammonium bromide as catalyst and potassium carbonate as base (Scheme 1).

In the title compound, the heterocyclic ring has puckering parameters Q = 0.6272 (10) Å, θ = 63.91 (10)° and φ = 325.56 (11)°. The dihedral angle between the rings C1-C6 and C10-C15 is 86.54 (4)°. Weak C—H···O interactions (Table 1) form chains running parallel to the b axis (Fig. 2).

Related literature top

For related structures and background to 1,4-benzothiazine derivatives, see: Zerzouf et al. (2001); Sebbar et al. (2015).

Experimental top

To a solution of 2H-benzo[b][1,4]thiazin-3(4H)-one (0.543 g, 3.29 mmol), benzyl chloride (0.76 ml, 6.58 mmol) and potassium carbonate (0.91 g, 6.58 mmol) in DMF (15 ml) was added a catalytic amount of tetra- n-butylammonium bromide (0.11 g, 0.33 mmol) and the mixture was stirred for 24 h. The solid material was removed by filtration and the solvent evaporated under vacuum. The solid product was purified by recrystallization from ethanol to afford colorless crystals in 75% yield.

Structure description top

For related structures and background to 1,4-benzothiazine derivatives, see: Zerzouf et al. (2001); Sebbar et al. (2015).

Computing details top

Data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); 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, 2015b).

Figures top

	Fig. 1. Perspective view of the molecule with 50% probability ellipsoids.
	Fig. 2. Packing viewed down the b axis. Intermolecular C—H···O interactions are shown by dotted lines.

4-Benzyl-2H-benzo[b][1,4]thiazin-3(4H)-one top

Crystal data top

C₁₅H₁₃NOS	F(000) = 536
M_r = 255.32	D_x = 1.369 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.8711 (7) Å	Cell parameters from 9273 reflections
b = 5.3815 (3) Å	θ = 2.6–29.0°
c = 21.1997 (13) Å	µ = 0.25 mm⁻¹
β = 93.128 (1)°	T = 150 K
V = 1238.39 (13) Å³	Block, colourless
Z = 4	0.31 × 0.19 × 0.15 mm

Data collection top

Bruker SMART APEX CCD diffractometer	3318 independent reflections
Radiation source: fine-focus sealed tube	2731 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 8.3333 pixels mm^-1	θ_max = 29.1°, θ_min = 1.9°
φ and ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −7→7
T_min = 0.88, T_max = 0.96	l = −28→28
22588 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0711P)² + 0.0734P] where P = (F_o² + 2F_c²)/3
3318 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₅H₁₃NOS	V = 1238.39 (13) Å³
M_r = 255.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.8711 (7) Å	µ = 0.25 mm⁻¹
b = 5.3815 (3) Å	T = 150 K
c = 21.1997 (13) Å	0.31 × 0.19 × 0.15 mm
β = 93.128 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	3318 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2015)	2731 reflections with I > 2σ(I)
T_min = 0.88, T_max = 0.96	R_int = 0.034
22588 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.06	Δρ_max = 0.43 e Å⁻³
3318 reflections	Δρ_min = −0.19 e Å⁻³
163 parameters

Special details top

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, colllected at φ = 0.00, 90.00 and 180.00° and 2 sets of 800 frames, each of width 0.45° in φ, collected at ω = –30.00 and 210.00°. The scan time was 20 sec/frame.

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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å). All were included as riding contributions with isotropic displacement parameters 1.2 times those of the attached atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	1.01122 (3)	0.51867 (6)	0.64271 (2)	0.02520 (11)
O1	0.82014 (8)	0.06255 (17)	0.72781 (4)	0.0263 (2)
N1	0.77044 (9)	0.22455 (18)	0.63087 (4)	0.0188 (2)
C1	0.78669 (10)	0.4044 (2)	0.58307 (5)	0.0183 (2)
C2	0.69629 (11)	0.4345 (2)	0.53375 (5)	0.0228 (2)
H2	0.6216	0.3430	0.5342	0.027*
C3	0.71505 (12)	0.5966 (2)	0.48439 (5)	0.0266 (3)
H3	0.6537	0.6136	0.4510	0.032*
C4	0.82274 (12)	0.7341 (2)	0.48348 (5)	0.0283 (3)
H4	0.8359	0.8435	0.4493	0.034*
C5	0.91096 (12)	0.7109 (3)	0.53267 (5)	0.0273 (3)
H5	0.9839	0.8080	0.5325	0.033*
C6	0.89443 (10)	0.5470 (2)	0.58242 (5)	0.0204 (2)
C7	0.90903 (11)	0.4571 (2)	0.70494 (5)	0.0202 (2)
H7A	0.9579	0.4299	0.7451	0.024*
H7B	0.8549	0.6026	0.7104	0.024*
C8	0.83135 (10)	0.2310 (2)	0.68959 (5)	0.0191 (2)
C9	0.68427 (11)	0.0192 (2)	0.61862 (6)	0.0206 (2)
H9A	0.7166	−0.1296	0.6415	0.025*
H9B	0.6814	−0.0193	0.5729	0.025*
C10	0.55414 (10)	0.0666 (2)	0.63773 (5)	0.0185 (2)
C11	0.52211 (11)	0.2662 (2)	0.67490 (5)	0.0239 (3)
H11	0.5828	0.3854	0.6879	0.029*
C12	0.40231 (12)	0.2935 (3)	0.69330 (5)	0.0290 (3)
H12	0.3813	0.4312	0.7186	0.035*
C13	0.31340 (12)	0.1201 (3)	0.67478 (6)	0.0302 (3)
H13	0.2314	0.1387	0.6874	0.036*
C14	0.34421 (12)	−0.0800 (3)	0.63797 (7)	0.0319 (3)
H14	0.2835	−0.1998	0.6255	0.038*
C15	0.46353 (11)	−0.1061 (2)	0.61924 (6)	0.0261 (3)
H15	0.4839	−0.2430	0.5935	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01580 (17)	0.0344 (2)	0.02528 (17)	−0.00305 (11)	−0.00034 (12)	0.00452 (11)
O1	0.0243 (4)	0.0259 (5)	0.0282 (4)	−0.0015 (4)	−0.0014 (3)	0.0087 (3)
N1	0.0177 (4)	0.0169 (5)	0.0215 (4)	−0.0014 (4)	−0.0006 (3)	−0.0006 (3)
C1	0.0192 (5)	0.0181 (5)	0.0178 (5)	0.0024 (4)	0.0019 (4)	−0.0025 (4)
C2	0.0227 (6)	0.0244 (6)	0.0210 (5)	−0.0001 (5)	−0.0022 (4)	−0.0040 (4)
C3	0.0296 (6)	0.0309 (7)	0.0189 (5)	0.0040 (5)	−0.0033 (5)	−0.0025 (5)
C4	0.0343 (7)	0.0302 (7)	0.0209 (5)	0.0020 (5)	0.0051 (5)	0.0054 (5)
C5	0.0243 (6)	0.0318 (7)	0.0263 (6)	−0.0026 (5)	0.0060 (5)	0.0039 (5)
C6	0.0171 (5)	0.0245 (6)	0.0198 (5)	0.0022 (4)	0.0019 (4)	−0.0011 (4)
C7	0.0200 (5)	0.0219 (6)	0.0186 (5)	−0.0010 (4)	−0.0006 (4)	0.0009 (4)
C8	0.0157 (5)	0.0195 (6)	0.0220 (5)	0.0034 (4)	0.0011 (4)	0.0006 (4)
C9	0.0195 (6)	0.0145 (5)	0.0276 (6)	−0.0002 (4)	0.0003 (4)	−0.0032 (4)
C10	0.0187 (5)	0.0167 (5)	0.0200 (5)	0.0008 (4)	−0.0010 (4)	0.0021 (4)
C11	0.0239 (6)	0.0234 (6)	0.0242 (5)	0.0017 (5)	−0.0014 (4)	−0.0022 (4)
C12	0.0302 (7)	0.0345 (7)	0.0228 (5)	0.0097 (6)	0.0050 (5)	−0.0008 (5)
C13	0.0218 (6)	0.0410 (8)	0.0283 (6)	0.0048 (5)	0.0055 (5)	0.0115 (6)
C14	0.0218 (6)	0.0306 (7)	0.0430 (7)	−0.0051 (5)	−0.0014 (5)	0.0061 (6)
C15	0.0236 (6)	0.0196 (6)	0.0349 (6)	−0.0012 (5)	−0.0004 (5)	−0.0023 (5)

Geometric parameters (Å, º) top

S1—C6	1.7583 (11)	C7—H7A	0.9900
S1—C7	1.8013 (12)	C7—H7B	0.9900
O1—C8	1.2262 (14)	C9—C10	1.5144 (16)
N1—C8	1.3781 (13)	C9—H9A	0.9900
N1—C1	1.4191 (14)	C9—H9B	0.9900
N1—C9	1.4628 (14)	C10—C11	1.3880 (16)
C1—C6	1.4012 (16)	C10—C15	1.3947 (16)
C1—C2	1.4047 (15)	C11—C12	1.3876 (17)
C2—C3	1.3860 (18)	C11—H11	0.9500
C2—H2	0.9500	C12—C13	1.3848 (19)
C3—C4	1.3859 (19)	C12—H12	0.9500
C3—H3	0.9500	C13—C14	1.382 (2)
C4—C5	1.3833 (16)	C13—H13	0.9500
C4—H4	0.9500	C14—C15	1.3843 (18)
C5—C6	1.3940 (17)	C14—H14	0.9500
C5—H5	0.9500	C15—H15	0.9500
C7—C8	1.5066 (16)

C6—S1—C7	95.66 (5)	O1—C8—N1	121.21 (10)
C8—N1—C1	123.74 (9)	O1—C8—C7	121.93 (10)
C8—N1—C9	116.79 (9)	N1—C8—C7	116.84 (9)
C1—N1—C9	119.46 (9)	N1—C9—C10	115.07 (9)
C6—C1—C2	118.72 (10)	N1—C9—H9A	108.5
C6—C1—N1	121.15 (9)	C10—C9—H9A	108.5
C2—C1—N1	120.07 (10)	N1—C9—H9B	108.5
C3—C2—C1	120.60 (11)	C10—C9—H9B	108.5
C3—C2—H2	119.7	H9A—C9—H9B	107.5
C1—C2—H2	119.7	C11—C10—C15	118.70 (11)
C4—C3—C2	120.38 (11)	C11—C10—C9	123.32 (10)
C4—C3—H3	119.8	C15—C10—C9	117.92 (10)
C2—C3—H3	119.8	C12—C11—C10	120.65 (12)
C5—C4—C3	119.52 (11)	C12—C11—H11	119.7
C5—C4—H4	120.2	C10—C11—H11	119.7
C3—C4—H4	120.2	C13—C12—C11	120.02 (12)
C4—C5—C6	121.00 (12)	C13—C12—H12	120.0
C4—C5—H5	119.5	C11—C12—H12	120.0
C6—C5—H5	119.5	C14—C13—C12	119.89 (12)
C5—C6—C1	119.76 (10)	C14—C13—H13	120.1
C5—C6—S1	119.15 (9)	C12—C13—H13	120.1
C1—C6—S1	121.08 (9)	C13—C14—C15	120.04 (12)
C8—C7—S1	110.56 (8)	C13—C14—H14	120.0
C8—C7—H7A	109.5	C15—C14—H14	120.0
S1—C7—H7A	109.5	C14—C15—C10	120.69 (12)
C8—C7—H7B	109.5	C14—C15—H15	119.7
S1—C7—H7B	109.5	C10—C15—H15	119.7
H7A—C7—H7B	108.1

C8—N1—C1—C6	23.43 (16)	C1—N1—C8—O1	−175.23 (10)
C9—N1—C1—C6	−156.89 (11)	C9—N1—C8—O1	5.09 (15)
C8—N1—C1—C2	−159.32 (11)	C1—N1—C8—C7	6.40 (15)
C9—N1—C1—C2	20.36 (15)	C9—N1—C8—C7	−173.29 (10)
C6—C1—C2—C3	1.99 (17)	S1—C7—C8—O1	131.04 (10)
N1—C1—C2—C3	−175.32 (11)	S1—C7—C8—N1	−50.60 (12)
C1—C2—C3—C4	−0.93 (19)	C8—N1—C9—C10	88.08 (12)
C2—C3—C4—C5	−0.81 (19)	C1—N1—C9—C10	−91.62 (12)
C3—C4—C5—C6	1.48 (19)	N1—C9—C10—C11	−12.01 (16)
C4—C5—C6—C1	−0.40 (19)	N1—C9—C10—C15	170.98 (10)
C4—C5—C6—S1	178.35 (10)	C15—C10—C11—C12	0.00 (17)
C2—C1—C6—C5	−1.33 (17)	C9—C10—C11—C12	−176.99 (11)
N1—C1—C6—C5	175.96 (11)	C10—C11—C12—C13	0.24 (18)
C2—C1—C6—S1	179.95 (9)	C11—C12—C13—C14	0.01 (18)
N1—C1—C6—S1	−2.77 (15)	C12—C13—C14—C15	−0.51 (19)
C7—S1—C6—C5	147.46 (11)	C13—C14—C15—C10	0.75 (19)
C7—S1—C6—C1	−33.80 (10)	C11—C10—C15—C14	−0.49 (18)
C6—S1—C7—C8	57.87 (9)	C9—C10—C15—C14	176.66 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O1ⁱ	0.99	2.55	3.2504 (14)	128
C7—H7B···O1ⁱⁱ	0.99	2.53	3.4403 (15)	152

Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) x, y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O1ⁱ	0.99	2.55	3.2504 (14)	128
C7—H7B···O1ⁱⁱ	0.99	2.53	3.4403 (15)	152

Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) x, y+1, z.

Footnotes

‡Correspondence email: younes.ouzidan@usmba.ac.ma.

Acknowledgements

JTM thanks Tulane University for support of the Tulane Crystallography Laboratory.

References

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