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

Abstract

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.

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 ▸).

Experimental  

Crystal data  

• C₁₅H₁₃NS

• M _r = 239.33

• Monoclinic,

• a = 15.1241 (9) Å

• b = 6.0111 (4) Å

• c = 14.3212 (9) Å

• β = 110.268 (2)°

• V = 1221.36 (13) ų

• Z = 4

• Cu Kα radiation

• μ = 2.13 mm⁻¹

• T = 293 K

• 0.30 × 0.25 × 0.20 mm

Data collection  

• Bruker X8 Proteum diffractometer

• 10379 measured reflections

• 1988 independent reflections

• 1890 reflections with I > 2σ(I)

• R _int = 0.041

Refinement  

• R[F ² > 2σ(F ²)] = 0.036

• wR(F ²) = 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

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.

Supplementary Material

CCDC reference: 1039090

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

Cg is the centroid of the C3/C2/C7C10 ring.

DHA	DH	HA	D A	DHA
C7H7Cg i	0.93	2.75	3.485(2)	136

Symmetry code: (i) .

supplementary crystallographic information

S1. Comment

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.

S2. Experimental

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.

S3. Refinement

All H atoms were positioned geometrically and allowed to ride on their parent atom, with C—H = 0.93–0.97 Å, and with U_iso(H) = 1.2–1.5U_eq(C).

Figures

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.

Crystal data

C15H13NS	F(000) = 504
Mr = 239.33	Dx = 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

Bruker X8 Proteum diffractometer	1890 reflections with I > 2σ(I)
Radiation source: Bruker MicroStar microfocus rotating anode	Rint = 0.041
Helios multilayer optics monochromator	θmax = 64.6°, θmin = 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

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(Fo2) + (0.0608P)2 + 0.3174P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
1988 reflections	Δρmax = 0.18 e Å−3
156 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.