Crystal structure of 2-(4-methyl­phen­yl)-4H-1,3-benzo­thia­zine

Sandhya, N.C.; Chandra; Suresha, G.P.; Lokanath, N.K.; Mahendra, M.

doi:10.1107/S205698901402725X

organic compounds

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Volume 71| Part 2| February 2015| Page o74

doi:10.1107/S205698901402725X

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Crystal structure of 2-(4-methylphenyl)-4H-1,3-benzothiazine

N. C. Sandhya,^a Chandra,^b G. P. Suresha,^a N. K. Lokanath ^b and M. Mahendra ^b ^*

^aDepartment of Studies in Chemistry, Manasagangotri, University of Mysore, Mysore 570 006, India, and ^bDepartment of Studies in Physics, Manasagangotri, University of Mysore, Mysore 570 006, India
^*Correspondence e-mail: mahendra@physics.uni-mysore.ac.in

Edited by H. Ishida, Okayama University, Japan (Received 29 November 2014; accepted 12 December 2014; online 3 January 2015)

In the title compound, C₁₅H₁₃NS, the thiazine ring adopts a boat conformation. The dihedral angle between the planes of the benzene ring of the benzothiazine unit and the tolyl ring is 19.52 (9)°. In the crystal, molecules are linked by weak C—H⋯π interactions into a tape structure along the b-axis direction.

Keywords: crystal structure; benzothiazine derivative; biological properties; C—H⋯π interactions.

CCDC reference: 1039090

1. Related literature

For the biological importance of benzothiazine derivatives, see: Ahmad et al. (2010 ); Gupta et al. (2002 ); Lazzeri et al. (2001 ); Parveen et al. (2014 ); Zia-ur-Rehman et al. (2006 ).

2. Experimental

2.1. Crystal data

C₁₅H₁₃NS
M_r = 239.33
Monoclinic, P 2₁ /c
a = 15.1241 (9) Å
b = 6.0111 (4) Å
c = 14.3212 (9) Å
β = 110.268 (2)°
V = 1221.36 (13) Å³
Z = 4
Cu Kα radiation
μ = 2.13 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

2.2. Data collection

Bruker X8 Proteum diffractometer
10379 measured reflections
1988 independent reflections
1890 reflections with I > 2σ(I)
R_int = 0.041

2.3. Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.102
S = 1.05
1988 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C3/C2/C7–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯Cgⁱ	0.93	2.75	3.485 (2)	136
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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: SHELXL97.

Supporting information

CCDC reference: 1039090

Crystal structure: contains datablocks global, I. DOI: 10.1107/S205698901402725X/is5385sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S205698901402725X/is5385Isup2.hkl

Supporting information file. DOI: 10.1107/S205698901402725X/is5385Isup3.cml

checkCIF report

Comment top

Benzothiazines have been found to posses versatile biological activities, such as analgesic (Gupta et al., 2002), anti bacterial (Zia-ur-Rehman et al., 2006) and antioxidant activities (Ahmad et al., 2010). Also, benzothiazine derivatives have shown activities for the treatment of asthmatic therapy (Lazzeri et al., 2001). Recently, 1,2-benzothiazine-1,1-dioxide and its derivatives were reported as aldose reductase inhibitors (Parveen et al., 2014). With this potential background of benzothiazine derivatives, we have synthesized the title compound to study its crystal structure.

In the title compound (Fig. 1), the mean plane of the benzothiazine moiety (S1/C2/C7–C10/C3/C4/N5/C6) makes a dihedral angle of 19.52 (9)° with the benzene ring (C11–C16). The central thiazine ring adopts a boat conformation with puckering parameter Q = 0.5848 (16) Å and ϕ = 183.41 (17)°, and the maximum deviation found on the puckered atom at C6 is -0.170 (2) Å. There are no classic hydrogen bonds. Instead, a weak C—H···π interaction is observed (C7—H7···Cgⁱ; Cg: C3/C2/C7–C10; Table 1). The molecular packing exhibits layered stacking when viewed down the b axis as shown in Fig. 2.

Related literature top

For the biological importance of benzothiazine derivatives, see: Ahmad et al. (2010); Gupta et al. (2002); Lazzeri et al. (2001); Parveen et al. (2014); Zia-ur-Rehman et al. (2006).

Experimental top

4-Methyl-N-[(phenylthio)methyl]benzamide was heated with POCl₃ (10 ml) on an oil bath for 1 h. The reaction mixture was cooled by treated with ice, neutralized with Na₂CO₃, and extracted with dichloromethane. The combined extracts were dried (Na₂SO₄) and solvent was evaporated off. The residue was recrystalized from hot ethanol to get crystals of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with 50% probability displacement ellipsoids. H atoms are drawn as spheres of arbitrary radii.
	Fig. 2. A packing diagram of the title compound viewed along the b axis.

2-(4-Methylphenyl)-4H-1,3-benzothiazine top

Crystal data top

C₁₅H₁₃NS	F(000) = 504
M_r = 239.33	D_x = 1.302 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 1988 reflections
a = 15.1241 (9) Å	θ = 3.1–64.6°
b = 6.0111 (4) Å	µ = 2.13 mm⁻¹
c = 14.3212 (9) Å	T = 293 K
β = 110.268 (2)°	Block, light yellow
V = 1221.36 (13) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker X8 Proteum diffractometer	1890 reflections with I > 2σ(I)
Radiation source: Bruker MicroStar microfocus rotating anode	R_int = 0.041
Helios multilayer optics monochromator	θ_max = 64.6°, θ_min = 3.1°
Detector resolution: 10.7 pixels mm^-1	h = −17→16
ϕ and ω scans	k = −3→6
10379 measured reflections	l = −16→16
1988 independent reflections

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)] = 0.036	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0608P)² + 0.3174P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
1988 reflections	Δρ_max = 0.18 e Å⁻³
156 parameters	Δρ_min = −0.20 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: 0.0063 (7)

Crystal data top

C₁₅H₁₃NS	V = 1221.36 (13) Å³
M_r = 239.33	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 15.1241 (9) Å	µ = 2.13 mm⁻¹
b = 6.0111 (4) Å	T = 293 K
c = 14.3212 (9) Å	0.30 × 0.25 × 0.20 mm
β = 110.268 (2)°

Data collection top

Bruker X8 Proteum diffractometer	1890 reflections with I > 2σ(I)
10379 measured reflections	R_int = 0.041
1988 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.05	Δρ_max = 0.18 e Å⁻³
1988 reflections	Δρ_min = −0.20 e Å⁻³
156 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	0.85647 (3)	0.07017 (7)	0.54278 (3)	0.0440 (2)
N5	0.71804 (10)	−0.2361 (2)	0.51727 (10)	0.0482 (5)
C2	0.87171 (11)	0.0058 (3)	0.66754 (11)	0.0383 (5)
C3	0.83561 (11)	−0.1929 (3)	0.68916 (12)	0.0422 (5)
C4	0.78453 (13)	−0.3459 (3)	0.60484 (13)	0.0519 (6)
C6	0.74506 (11)	−0.0644 (2)	0.48288 (12)	0.0394 (5)
C7	0.92024 (12)	0.1532 (3)	0.74273 (12)	0.0461 (5)
C8	0.93470 (13)	0.0983 (3)	0.84074 (13)	0.0554 (6)
C9	0.90031 (14)	−0.0989 (4)	0.86320 (14)	0.0595 (7)
C10	0.85010 (12)	−0.2426 (3)	0.78801 (13)	0.0534 (6)
C11	0.68996 (11)	0.0295 (3)	0.38404 (12)	0.0399 (5)
C12	0.70649 (13)	0.2415 (3)	0.35473 (13)	0.0494 (6)
C13	0.66238 (14)	0.3119 (3)	0.25780 (14)	0.0548 (6)
C14	0.59980 (13)	0.1777 (3)	0.18745 (13)	0.0520 (6)
C15	0.58033 (14)	−0.0299 (3)	0.21806 (14)	0.0577 (6)
C16	0.62461 (13)	−0.1037 (3)	0.31386 (13)	0.0501 (6)
C17	0.55616 (18)	0.2545 (4)	0.08089 (15)	0.0766 (8)
H4A	0.83080	−0.42520	0.58460	0.0620*
H4B	0.75040	−0.45520	0.62890	0.0620*
H7	0.94270	0.28720	0.72730	0.0550*
H8	0.96770	0.19490	0.89160	0.0660*
H9	0.91090	−0.13580	0.92930	0.0710*
H10	0.82580	−0.37380	0.80390	0.0640*
H12	0.74760	0.33660	0.40080	0.0590*
H13	0.67520	0.45350	0.23960	0.0660*
H15	0.53630	−0.12110	0.17280	0.0690*
H16	0.61070	−0.24440	0.33200	0.0600*
H17A	0.56570	0.41170	0.07730	0.1150*
H17B	0.48980	0.22310	0.05730	0.1150*
H17C	0.58520	0.17760	0.04030	0.1150*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0437 (3)	0.0489 (3)	0.0373 (3)	−0.0101 (2)	0.0113 (2)	0.0032 (2)
N5	0.0492 (8)	0.0407 (8)	0.0485 (8)	−0.0079 (6)	0.0092 (6)	0.0025 (6)
C2	0.0358 (8)	0.0401 (8)	0.0380 (8)	0.0031 (7)	0.0117 (6)	0.0024 (7)
C3	0.0395 (8)	0.0430 (9)	0.0442 (9)	0.0027 (7)	0.0145 (7)	0.0064 (7)
C4	0.0598 (11)	0.0388 (10)	0.0518 (10)	−0.0056 (8)	0.0127 (8)	0.0080 (8)
C6	0.0402 (9)	0.0373 (9)	0.0396 (8)	−0.0010 (6)	0.0126 (7)	−0.0030 (6)
C7	0.0434 (9)	0.0466 (10)	0.0428 (9)	0.0001 (7)	0.0081 (7)	−0.0009 (7)
C8	0.0515 (11)	0.0685 (12)	0.0395 (9)	0.0058 (9)	0.0074 (8)	−0.0055 (8)
C9	0.0585 (11)	0.0820 (14)	0.0385 (9)	0.0096 (10)	0.0174 (9)	0.0103 (9)
C10	0.0514 (10)	0.0612 (12)	0.0497 (10)	0.0034 (9)	0.0203 (8)	0.0177 (9)
C11	0.0392 (8)	0.0393 (9)	0.0405 (9)	0.0006 (7)	0.0128 (7)	−0.0015 (7)
C12	0.0546 (10)	0.0414 (10)	0.0449 (9)	−0.0046 (8)	0.0078 (8)	−0.0011 (7)
C13	0.0610 (11)	0.0452 (10)	0.0533 (10)	0.0016 (8)	0.0135 (9)	0.0084 (8)
C14	0.0480 (10)	0.0587 (11)	0.0440 (9)	0.0060 (8)	0.0091 (8)	0.0053 (8)
C15	0.0520 (11)	0.0627 (12)	0.0461 (10)	−0.0094 (9)	0.0014 (8)	−0.0031 (9)
C16	0.0487 (10)	0.0453 (10)	0.0500 (10)	−0.0075 (8)	0.0092 (8)	0.0003 (8)
C17	0.0780 (15)	0.0877 (16)	0.0494 (11)	0.0016 (12)	0.0035 (10)	0.0156 (11)

Geometric parameters (Å, º) top

S1—C2	1.7635 (16)	C14—C15	1.388 (3)
S1—C6	1.7967 (17)	C14—C17	1.510 (3)
N5—C4	1.465 (2)	C15—C16	1.375 (3)
N5—C6	1.2705 (19)	C4—H4A	0.9700
C2—C3	1.392 (3)	C4—H4B	0.9700
C2—C7	1.391 (2)	C7—H7	0.9300
C3—C4	1.502 (2)	C8—H8	0.9300
C3—C10	1.388 (2)	C9—H9	0.9300
C6—C11	1.483 (2)	C10—H10	0.9300
C7—C8	1.384 (2)	C12—H12	0.9300
C8—C9	1.377 (3)	C13—H13	0.9300
C9—C10	1.384 (3)	C15—H15	0.9300
C11—C12	1.391 (3)	C16—H16	0.9300
C11—C16	1.393 (3)	C17—H17A	0.9600
C12—C13	1.382 (3)	C17—H17B	0.9600
C13—C14	1.379 (3)	C17—H17C	0.9600

C2—S1—C6	99.02 (8)	N5—C4—H4B	109.00
C4—N5—C6	118.70 (15)	C3—C4—H4A	109.00
S1—C2—C3	119.34 (12)	C3—C4—H4B	109.00
S1—C2—C7	119.55 (13)	H4A—C4—H4B	108.00
C3—C2—C7	121.11 (15)	C2—C7—H7	120.00
C2—C3—C4	118.61 (14)	C8—C7—H7	120.00
C2—C3—C10	118.43 (15)	C7—C8—H8	120.00
C4—C3—C10	122.95 (16)	C9—C8—H8	120.00
N5—C4—C3	114.95 (14)	C8—C9—H9	120.00
S1—C6—N5	123.71 (13)	C10—C9—H9	120.00
S1—C6—C11	114.10 (11)	C3—C10—H10	120.00
N5—C6—C11	121.96 (15)	C9—C10—H10	120.00
C2—C7—C8	119.27 (17)	C11—C12—H12	120.00
C7—C8—C9	120.18 (17)	C13—C12—H12	120.00
C8—C9—C10	120.36 (17)	C12—C13—H13	119.00
C3—C10—C9	120.62 (17)	C14—C13—H13	119.00
C6—C11—C12	122.43 (15)	C14—C15—H15	119.00
C6—C11—C16	119.58 (15)	C16—C15—H15	119.00
C12—C11—C16	117.75 (16)	C11—C16—H16	120.00
C11—C12—C13	120.59 (17)	C15—C16—H16	120.00
C12—C13—C14	121.68 (17)	C14—C17—H17A	110.00
C13—C14—C15	117.54 (17)	C14—C17—H17B	109.00
C13—C14—C17	120.58 (18)	C14—C17—H17C	109.00
C15—C14—C17	121.87 (18)	H17A—C17—H17B	109.00
C14—C15—C16	121.47 (18)	H17A—C17—H17C	109.00
C11—C16—C15	120.87 (17)	H17B—C17—H17C	110.00
N5—C4—H4A	109.00

C6—S1—C2—C3	31.75 (16)	S1—C6—C11—C12	−20.0 (2)
C6—S1—C2—C7	−148.81 (15)	S1—C6—C11—C16	154.33 (14)
C2—S1—C6—N5	−30.02 (16)	N5—C6—C11—C12	165.34 (17)
C2—S1—C6—C11	155.37 (12)	N5—C6—C11—C16	−20.4 (3)
C6—N5—C4—C3	47.9 (2)	C2—C7—C8—C9	−0.8 (3)
C4—N5—C6—S1	−6.7 (2)	C7—C8—C9—C10	−0.8 (3)
C4—N5—C6—C11	167.49 (15)	C8—C9—C10—C3	1.6 (3)
S1—C2—C3—C4	−0.1 (2)	C6—C11—C12—C13	171.49 (18)
S1—C2—C3—C10	178.66 (14)	C16—C11—C12—C13	−2.9 (3)
C7—C2—C3—C4	−179.54 (17)	C6—C11—C16—C15	−172.56 (18)
C3—C2—C7—C8	1.6 (3)	C12—C11—C16—C15	2.0 (3)
C7—C2—C3—C10	−0.8 (3)	C11—C12—C13—C14	1.0 (3)
S1—C2—C7—C8	−177.85 (15)	C12—C13—C14—C15	1.8 (3)
C2—C3—C4—N5	−43.9 (2)	C12—C13—C14—C17	−177.1 (2)
C10—C3—C4—N5	137.37 (18)	C13—C14—C15—C16	−2.7 (3)
C2—C3—C10—C9	−0.8 (3)	C17—C14—C15—C16	176.1 (2)
C4—C3—C10—C9	177.91 (19)	C14—C15—C16—C11	0.8 (3)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C3/C2/C7–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Cgⁱ	0.93	2.75	3.485 (2)	136

Symmetry code: (i) −x, y+1/2, −z−1/2.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C3/C2/C7–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Cgⁱ	0.93	2.75	3.485 (2)	136

Symmetry code: (i) −x, y+1/2, −z−1/2.

Acknowledgements

MM would like to thank the UGC, New Delhi, Government of India, for the award of a project under the head F. No. 41–920/2012(SR) dated: 25-07-2012.

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