3-(2-Methyl­benzyl­idene)-2,3-dihydro-1,5-benzothia­zepin-4(5H)-one

Sridevi, D.; Bhaskaran, S.; Usha, G.; Murugan, G.; Bakthadoss, M.

doi:10.1107/S1600536810052888

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o243

doi:10.1107/S1600536810052888

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3-(2-Methylbenzylidene)-2,3-dihydro-1,5-benzothiazepin-4(5H)-one

D. Sridevi,^a Sundari Bhaskaran,^a G. Usha,^a ^* G. Murugan ^b and M. Bakthadoss ^b

^aDepartment of Physics, Queen Mary's College(A), Chennai-4, Tamilnadu, India, and ^bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai-25, India
^*Correspondence e-mail: guqmc@yahoo.com

(Received 26 November 2010; accepted 16 December 2010; online 8 January 2011)

In the crystal structure of the title compound, C₁₇H₁₅NOS, the molecules form centrosymmetric dimers through pairs of N—H⋯O hydrogen bonds. The seven-membered ring adopts a distorted half-chair conformation.

Related literature

Dibenzo[c,e]thiepine derivatives exhibit chiroptical properties (Tomascovic et al., 2000 ) and dibenzo[b,e]thiepin-5,5-dioxide derivatives possess antihistaminic and antiallergenic activities (Rajsner et al., 1971 ) while benzene thiepine derivatives have been identified as effective antihistaminic compounds (Metys et al., 1965 ).

Experimental

Crystal data

C₁₇H₁₅NOS
M_r = 281.36
Monoclinic, C 2/c
a = 19.1192 (5) Å
b = 13.0049 (3) Å
c = 14.8903 (4) Å
β = 128.591 (1)°
V = 2893.84 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 293 K
0.22 × 0.18 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
13879 measured reflections
3560 independent reflections
2707 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.202
S = 0.83
3560 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H0⋯Oⁱ	0.86	2.01	2.8705 (18)	177
Symmetry code: (i) -x, -y+1, -z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810052888/bt5422sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810052888/bt5422Isup2.hkl

checkCIF report

Comment top

The title compound is used as an intermediate for the synthesis of dosulepin, which is an antidepressant of the tricyclic family. Dosulepin prevents reabsorbing of serotonin and noradrenaline in the brain, helps to prolong the mood lightening effect of any released noradrenaline and serotonin, thus relieving depression. The dibenzo[c,e]thiepine derivatives exhibit chiroptical properties (Tomascovic et al., 2000). Dibenzo[b,e]thiepin-5,5-dioxide derivatives possess antihistaminic and antiallergenic activities (Rajsner et al., 1971). Benzene thiepine derivatives are identified as a new type of effective antihistaminic compounds (Metys et al., 1965). Considering the wide range of biological activities of the thiepine derivatives, we determined the crystal structure of the title compound. The seven membered thiepin ring adopts a distorted half-chair conformation. The molecules form centrosymmetric dimers through N—H···O hydrogen bonds.

Related literature top

Dibenzo[c,e]thiepine derivatives exhibit chiroptical properties (Tomascovic et al., 2000) and dibenzo[b,e]thiepin-5,5-dioxide derivatives possess antihistaminic and antiallergenic activities (Rajsner et al., 1971) while benzene thiepine derivatives have been identified as effective antihistaminic compounds (Metys et al., 1965).

Experimental top

A mixture of(Z)-methyl 2-(bromomethyl)-3-o-tolylacrylate (2 mmol) and o-aminothiophenol(2 mmol) in the presence of potassium tert-butoxide (2.4 mmol) in dry THF (10 ml) was stirred at room temperature for 1 h. After the completion of the reaction as indicated by TLC, the reaction mixture was concentrated and the resulting crude mass was diluted with water (20 ml) and extracted with ethyl acetate (3 x 20ml). The organic layer was washed with brine (2 x 20ml) and dried over anhydrous sodium sulfate. The organic layer was concentrated, which provided a crude mass (Z)-methyl 2-((2-aminophenylthio)methyl)-3-o-tolylacrylate. The crude product was treated with a catalytic amount of p-toluene sulphonic acid (0.4 mmol), in p-xylene (10 ml), under reflux conditions for 12 h. After the completion of the reaction as indicated by TLC, the reaction mixture was concentrated under reduced pressure and worked up as mentioned previously, which successfully provide the crude final product. The final product was purified by column chromatography on silica gel to afford the title compound in good yield (67%).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Perspective view of the title compound with 30% probability ellipsoids.
	Fig. 2. Partial packing diagram, viewed along the c axis.

3-(2-Methylbenzylidene)-2,3-dihydro-1,5-benzothiazepin-4(5H)-one top

Crystal data top

C₁₇H₁₅NOS	F(000) = 1184
M_r = 281.36	D_x = 1.292 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.1192 (5) Å	Cell parameters from 3560 reflections
b = 13.0049 (3) Å	θ = 2–28°
c = 14.8903 (4) Å	µ = 0.22 mm⁻¹
β = 128.591 (1)°	T = 293 K
V = 2893.84 (13) Å³	Block, colourless
Z = 8	0.22 × 0.18 × 0.18 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2707 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 28.4°, θ_min = 2.1°
ω and ϕ scans	h = −25→20
13879 measured reflections	k = −15→16
3560 independent reflections	l = −15→19

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.202	H-atom parameters constrained
S = 0.83	w = 1/[σ²(F_o²) + (0.2P)²] where P = (F_o² + 2F_c²)/3
3560 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³
0 constraints

Crystal data top

C₁₇H₁₅NOS	V = 2893.84 (13) Å³
M_r = 281.36	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 19.1192 (5) Å	µ = 0.22 mm⁻¹
b = 13.0049 (3) Å	T = 293 K
c = 14.8903 (4) Å	0.22 × 0.18 × 0.18 mm
β = 128.591 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2707 reflections with I > 2σ(I)
13879 measured reflections	R_int = 0.024
3560 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.202	H-atom parameters constrained
S = 0.83	Δρ_max = 0.27 e Å⁻³
3560 reflections	Δρ_min = −0.30 e Å⁻³
181 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	0.07250 (13)	0.88179 (15)	0.21097 (16)	0.0540 (5)
H1	0.1146	0.9233	0.2730	0.065*
C2	−0.00643 (15)	0.92462 (17)	0.11794 (18)	0.0623 (5)
H2	−0.0169	0.9947	0.1164	0.075*
C3	−0.06956 (12)	0.86298 (15)	0.02748 (16)	0.0557 (5)
H3	−0.1233	0.8912	−0.0351	0.067*
C4	−0.05362 (11)	0.75966 (14)	0.02896 (14)	0.0448 (4)
H4	−0.0970	0.7185	−0.0326	0.054*
C5	0.02685 (10)	0.71567 (12)	0.12171 (12)	0.0365 (4)
C6	0.08537 (12)	0.52859 (14)	0.17690 (13)	0.0485 (4)
C7	0.14280 (11)	0.52918 (13)	0.30555 (12)	0.0424 (4)
C8	0.15581 (12)	0.62540 (13)	0.36935 (13)	0.0478 (4)
H8A	0.1988	0.6123	0.4512	0.057*
H8B	0.0995	0.6441	0.3523	0.057*
C9	0.09042 (10)	0.77806 (13)	0.21391 (13)	0.0398 (4)
C10	0.18328 (12)	0.44083 (13)	0.35720 (14)	0.0477 (4)
H10	0.1742	0.3876	0.3092	0.057*
C11	0.24053 (11)	0.41648 (13)	0.48045 (14)	0.0449 (4)
C12	0.21413 (14)	0.43985 (16)	0.54648 (16)	0.0573 (5)
H12	0.1612	0.4759	0.5135	0.069*
C13	0.26536 (17)	0.4103 (2)	0.66057 (18)	0.0723 (7)
H13	0.2472	0.4269	0.7040	0.087*
C14	0.34253 (16)	0.35663 (19)	0.70886 (18)	0.0750 (7)
H14	0.3770	0.3360	0.7853	0.090*
C15	0.36932 (13)	0.33310 (17)	0.64501 (18)	0.0676 (6)
H15	0.4222	0.2966	0.6792	0.081*
C16	0.31970 (11)	0.36225 (14)	0.52991 (15)	0.0504 (4)
C17	0.35129 (16)	0.33506 (19)	0.4639 (2)	0.0722 (6)
H17A	0.4068	0.2983	0.5126	0.108*
H17B	0.3601	0.3967	0.4366	0.108*
H17C	0.3074	0.2926	0.3997	0.108*
N	0.03793 (9)	0.61072 (12)	0.10949 (10)	0.0450 (4)
H0	0.0047	0.5939	0.0381	0.054*
O	0.07844 (12)	0.44836 (11)	0.12814 (11)	0.0766 (5)
S1	0.19459 (3)	0.73150 (4)	0.33323 (3)	0.0503 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0582 (10)	0.0419 (10)	0.0457 (9)	−0.0007 (8)	0.0246 (8)	−0.0069 (7)
C2	0.0737 (12)	0.0426 (10)	0.0558 (11)	0.0134 (8)	0.0332 (10)	0.0055 (8)
C3	0.0507 (9)	0.0560 (12)	0.0456 (10)	0.0109 (8)	0.0228 (8)	0.0110 (8)
C4	0.0400 (8)	0.0503 (10)	0.0332 (8)	−0.0013 (6)	0.0174 (7)	0.0027 (6)
C5	0.0373 (7)	0.0405 (8)	0.0284 (7)	−0.0002 (6)	0.0190 (6)	0.0005 (6)
C6	0.0570 (9)	0.0436 (10)	0.0281 (7)	0.0032 (7)	0.0183 (7)	−0.0047 (6)
C7	0.0501 (8)	0.0414 (9)	0.0262 (7)	0.0001 (7)	0.0192 (6)	−0.0041 (6)
C8	0.0600 (9)	0.0448 (10)	0.0258 (7)	0.0080 (7)	0.0205 (7)	−0.0024 (6)
C9	0.0391 (7)	0.0424 (9)	0.0305 (7)	0.0003 (6)	0.0180 (6)	0.0004 (6)
C10	0.0579 (9)	0.0426 (10)	0.0323 (8)	−0.0020 (7)	0.0231 (8)	−0.0030 (7)
C11	0.0497 (8)	0.0391 (9)	0.0345 (8)	−0.0061 (6)	0.0207 (7)	0.0027 (6)
C12	0.0610 (10)	0.0628 (13)	0.0444 (10)	−0.0029 (9)	0.0310 (9)	0.0050 (8)
C13	0.0867 (16)	0.0852 (17)	0.0483 (11)	−0.0180 (12)	0.0438 (12)	0.0024 (11)
C14	0.0811 (14)	0.0757 (16)	0.0366 (9)	−0.0188 (12)	0.0211 (10)	0.0107 (9)
C15	0.0500 (9)	0.0583 (13)	0.0547 (12)	−0.0067 (8)	0.0131 (9)	0.0079 (9)
C16	0.0489 (8)	0.0429 (10)	0.0442 (9)	−0.0116 (7)	0.0217 (8)	−0.0030 (7)
C17	0.0664 (12)	0.0654 (14)	0.0809 (16)	−0.0040 (10)	0.0441 (12)	−0.0149 (11)
N	0.0499 (7)	0.0433 (8)	0.0229 (6)	0.0019 (6)	0.0135 (6)	−0.0046 (5)
O	0.1042 (12)	0.0492 (9)	0.0302 (6)	0.0191 (8)	0.0193 (7)	−0.0072 (5)
S1	0.0394 (3)	0.0464 (3)	0.0371 (3)	−0.00100 (15)	0.0101 (2)	−0.00664 (16)

Geometric parameters (Å, º) top

C1—C2	1.378 (3)	C9—S1	1.7538 (16)
C1—C9	1.386 (2)	C10—C11	1.470 (2)
C1—H1	0.9300	C10—H10	0.9300
C2—C3	1.373 (3)	C11—C16	1.393 (3)
C2—H2	0.9300	C11—C12	1.390 (3)
C3—C4	1.375 (3)	C12—C13	1.385 (3)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.397 (2)	C13—C14	1.363 (3)
C4—H4	0.9300	C13—H13	0.9300
C5—C9	1.392 (2)	C14—C15	1.367 (4)
C5—N	1.410 (2)	C14—H14	0.9300
C6—O	1.230 (2)	C15—C16	1.397 (3)
C6—N	1.355 (2)	C15—H15	0.9300
C6—C7	1.501 (2)	C16—C17	1.482 (3)
C7—C10	1.330 (2)	C17—H17A	0.9600
C7—C8	1.495 (2)	C17—H17B	0.9600
C8—S1	1.8001 (19)	C17—H17C	0.9600
C8—H8A	0.9700	N—H0	0.8600
C8—H8B	0.9700

C2—C1—C9	121.29 (17)	C7—C10—H10	115.8
C2—C1—H1	119.4	C11—C10—H10	115.8
C9—C1—H1	119.4	C16—C11—C12	119.40 (16)
C3—C2—C1	119.44 (19)	C16—C11—C10	119.11 (17)
C3—C2—H2	120.3	C12—C11—C10	121.33 (17)
C1—C2—H2	120.3	C13—C12—C11	121.1 (2)
C2—C3—C4	120.29 (17)	C13—C12—H12	119.5
C2—C3—H3	119.9	C11—C12—H12	119.5
C4—C3—H3	119.9	C14—C13—C12	119.6 (2)
C3—C4—C5	120.83 (16)	C14—C13—H13	120.2
C3—C4—H4	119.6	C12—C13—H13	120.2
C5—C4—H4	119.6	C15—C14—C13	119.99 (19)
C9—C5—C4	118.81 (15)	C15—C14—H14	120.0
C9—C5—N	125.61 (14)	C13—C14—H14	120.0
C4—C5—N	115.48 (14)	C14—C15—C16	122.0 (2)
O—C6—N	117.10 (14)	C14—C15—H15	119.0
O—C6—C7	118.78 (15)	C16—C15—H15	119.0
N—C6—C7	124.09 (14)	C11—C16—C15	117.93 (19)
C10—C7—C8	123.34 (14)	C11—C16—C17	121.88 (18)
C10—C7—C6	115.63 (14)	C15—C16—C17	120.2 (2)
C8—C7—C6	120.97 (14)	C16—C17—H17A	109.5
C7—C8—S1	112.83 (12)	C16—C17—H17B	109.5
C7—C8—H8A	109.0	H17A—C17—H17B	109.5
S1—C8—H8A	109.0	C16—C17—H17C	109.5
C7—C8—H8B	109.0	H17A—C17—H17C	109.5
S1—C8—H8B	109.0	H17B—C17—H17C	109.5
H8A—C8—H8B	107.8	C6—N—C5	138.81 (13)
C1—C9—C5	119.31 (15)	C6—N—H0	110.6
C1—C9—S1	118.05 (13)	C5—N—H0	110.6
C5—C9—S1	122.61 (13)	C9—S1—C8	98.53 (8)
C7—C10—C11	128.30 (16)

C9—C1—C2—C3	1.6 (3)	C7—C10—C11—C12	49.1 (3)
C1—C2—C3—C4	−0.9 (3)	C16—C11—C12—C13	0.1 (3)
C2—C3—C4—C5	−0.3 (3)	C10—C11—C12—C13	175.39 (19)
C3—C4—C5—C9	1.0 (2)	C11—C12—C13—C14	−0.6 (3)
C3—C4—C5—N	−175.59 (16)	C12—C13—C14—C15	0.5 (4)
O—C6—C7—C10	0.9 (3)	C13—C14—C15—C16	−0.1 (3)
N—C6—C7—C10	178.94 (17)	C12—C11—C16—C15	0.3 (3)
O—C6—C7—C8	178.10 (19)	C10—C11—C16—C15	−175.08 (17)
N—C6—C7—C8	−3.8 (3)	C12—C11—C16—C17	179.97 (18)
C10—C7—C8—S1	123.26 (16)	C10—C11—C16—C17	4.6 (3)
C6—C7—C8—S1	−53.7 (2)	C14—C15—C16—C11	−0.3 (3)
C2—C1—C9—C5	−0.9 (3)	C14—C15—C16—C17	−180.0 (2)
C2—C1—C9—S1	177.38 (15)	O—C6—N—C5	−175.66 (19)
C4—C5—C9—C1	−0.4 (2)	C7—C6—N—C5	6.3 (3)
N—C5—C9—C1	175.84 (16)	C9—C5—N—C6	26.7 (3)
C4—C5—C9—S1	−178.59 (12)	C4—C5—N—C6	−157.0 (2)
N—C5—C9—S1	−2.4 (2)	C1—C9—S1—C8	128.73 (15)
C8—C7—C10—C11	5.3 (3)	C5—C9—S1—C8	−53.03 (15)
C6—C7—C10—C11	−177.56 (18)	C7—C8—S1—C9	87.11 (13)
C7—C10—C11—C16	−135.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0···Oⁱ	0.86	2.01	2.8705 (18)	177

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₅NOS
M_r	281.36
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	19.1192 (5), 13.0049 (3), 14.8903 (4)
β (°)	128.591 (1)
V (Å³)	2893.84 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.22 × 0.18 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	13879, 3560, 2707
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.202, 0.83
No. of reflections	3560
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.30

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0···Oⁱ	0.86	2.01	2.8705 (18)	177

Symmetry code: (i) −x, −y+1, −z.

Acknowledgements

The authors thank Professor D. Velmurugan, Centre for Advanced Study in Crystallography and Biophysics, University of Madras, for providing data-collection and computing facilities.

References

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