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

Chen, Z.-L.; Hong, F.; Zhao, S.-Y.

doi:10.1107/S1600536807062046

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o113

https://doi.org/10.1107/S1600536807062046

Open

access

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

Zhi-Long Chen,^a Feng Hong ^a and Sheng-Yin Zhao ^b ^*

^aInstitute of Biological Sciences and Biotechnology, Donghua University, Shanghai 201620, People's Republic of China, and ^bDepartment of Chemistry, Donghua University, Shanghai 201620, People's Republic of China
^*Correspondence e-mail: syzhao8@dhu.edu.cn

(Received 21 November 2007; accepted 22 November 2007; online 6 December 2007)

In the molecule of the title compound, C₉H₉NOS, the seven-membered ring has a twist conformation. In the crystal structure, intermolecular N—H⋯O hydrogen bonds link the molecules into centrosymmetric dimers.

Related literature

For general background, see: Arya et al. (1977 ). For related literature, see: Ishibashi et al. (2001 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₉NOS
M_r = 179.23
Orthorhombic, P b c a
a = 8.0510 (16) Å
b = 8.9580 (18) Å
c = 24.220 (5) Å
V = 1746.8 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 294 (2) K
0.20 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.939, T_max = 0.969
1704 measured reflections
1704 independent reflections
1089 reflections with I > 2σ(I)
R_int = 0.022
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.166
S = 1.02
1704 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H0A⋯Oⁱ	0.86	2.05	2.824 (4)	149
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius,1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo,1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens,1996 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807062046/hk2393sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062046/hk2393Isup2.hkl

checkCIF report

Comment top

The title compound, (I), is an important intermediate used in the synthesis of dipeptidyl peptidase-IV inhibitors, cysteine proteases inhibitors and antihypertensive agent (Arya et al., 1977). As part of our ongoing studies in this area, we report herein its synthesis and crystal structure.

In the molecule of (I), (Fig. 1) the bond lengths and angles are within normal ranges (Allen et al., 1987). Ring A (C3—C8) is, of course, planar, while ring B (S/N/C1—C3/C8/C9) is not planar and has a twisted conformation.

In the crystal structure, intermolecular N—H0A···Oⁱ hydrogen bonds [H0A···O 2.05 Å, N···O 2.824 (3) Å and N—H0A···O 149.4°] [symmetry code: (i) x + 1/2, 1/2 - y, -z] link the molecules into centrosymmetric dimers (Fig. 2), in which they seem to be effective in the stabilization of the structure.

Related literature top

For general background, see: Arya et al. (1977). For related literature, see: Ishibashi et al. (2001). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I), was prepared by the literature method with a minor change (Ishibashi et al., 2001). 2-Mercaptobenzoic acid methyl ester (3.3 g, 19.6 mmol) was added to the solution of sodium (0.5 g, 22.0 mmol) in ethanol (20 ml). The mixture was stirred at room temperature for 10 min, and then 2-oxazolidinone (1.7 g, 19.8 mmol) was added. The mixture was heated under reflux for 6 h. The solvent was evaporated off, water (15 ml) was added to the residue, and the whole mixture was extracted with ethyl acetate (15 ml×3). The combined ester layer was dried with sodium sulfate and evaporated. The residue was recrystallized from ethanol and dried in vacuum at 323 K to give the title compound as a white solid (yield; 60%, m.p. 466–468 K) (Ishibashi et al., 2001, m.p. 465–466 K). Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Structure description top

For general background, see: Arya et al. (1977). For related literature, see: Ishibashi et al. (2001). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius,1989); cell refinement: CAD-4 Software (Enraf–Nonius,1989); data reduction: XCAD4 (Harms & Wocadlo,1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens,1996); software used to prepare material for publication: SHELXL (Siemens,1996).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

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

Crystal data top

C₉H₉NOS	F(000) = 752
M_r = 179.23	D_x = 1.363 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 8.0510 (16) Å	θ = 9–13°
b = 8.9580 (18) Å	µ = 0.32 mm⁻¹
c = 24.220 (5) Å	T = 294 K
V = 1746.8 (6) Å³	Block, colorless
Z = 8	0.20 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1089 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 26.0°, θ_min = 1.7°
ω/2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
T_min = 0.939, T_max = 0.969	l = 0→29
1704 measured reflections	3 standard reflections every 120 min
1704 independent reflections	intensity decay: none

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.166	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.060P)² + 2.7P] where P = (F_o² + 2F_c²)/3
1704 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₉H₉NOS	V = 1746.8 (6) Å³
M_r = 179.23	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.0510 (16) Å	µ = 0.32 mm⁻¹
b = 8.9580 (18) Å	T = 294 K
c = 24.220 (5) Å	0.20 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1089 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.022
T_min = 0.939, T_max = 0.969	3 standard reflections every 120 min
1704 measured reflections	intensity decay: none
1704 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.166	H-atom parameters constrained
S = 1.02	Δρ_max = 0.23 e Å⁻³
1704 reflections	Δρ_min = −0.22 e Å⁻³
109 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
S	0.20239 (14)	0.28682 (12)	0.17431 (4)	0.0620 (4)
O	−0.0306 (4)	0.2669 (4)	0.02305 (13)	0.0753 (10)
N	0.2218 (4)	0.3438 (3)	0.04867 (12)	0.0452 (8)
H0A	0.2651	0.2918	0.0225	0.054*
C1	0.3328 (4)	0.4320 (4)	0.08290 (17)	0.0507 (10)
H1A	0.2801	0.5269	0.0911	0.061*
H1B	0.4336	0.4525	0.0623	0.061*
C2	0.3779 (5)	0.3569 (5)	0.1361 (2)	0.0674 (13)
H2A	0.4376	0.4275	0.1591	0.081*
H2B	0.4524	0.2746	0.1282	0.081*
C3	0.0396 (4)	0.4103 (4)	0.15575 (16)	0.0439 (9)
C4	−0.0452 (5)	0.4849 (5)	0.19751 (19)	0.0633 (12)
H4A	−0.0085	0.4768	0.2338	0.076*
C5	−0.1832 (6)	0.5708 (5)	0.1857 (2)	0.0695 (13)
H5A	−0.2375	0.6212	0.2140	0.083*
C6	−0.2398 (5)	0.5822 (5)	0.1333 (2)	0.0710 (14)
H6A	−0.3327	0.6402	0.1255	0.085*
C7	−0.1587 (4)	0.5068 (4)	0.09133 (18)	0.0518 (10)
H7A	−0.1988	0.5141	0.0554	0.062*
C8	−0.0196 (4)	0.4211 (4)	0.10152 (14)	0.0377 (8)
C9	0.0579 (4)	0.3377 (4)	0.05503 (16)	0.0449 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0642 (7)	0.0529 (7)	0.0691 (7)	0.0009 (6)	−0.0161 (5)	0.0134 (5)
O	0.0568 (18)	0.088 (2)	0.081 (2)	−0.0102 (17)	−0.0143 (16)	−0.0395 (18)
N	0.0378 (18)	0.0425 (17)	0.0553 (17)	0.0002 (15)	0.0038 (14)	−0.0121 (14)
C1	0.0335 (19)	0.040 (2)	0.079 (3)	−0.0057 (18)	0.0068 (18)	−0.014 (2)
C2	0.038 (2)	0.059 (3)	0.106 (4)	0.001 (2)	−0.013 (2)	0.000 (3)
C3	0.0356 (19)	0.0351 (19)	0.061 (2)	−0.0092 (17)	0.0057 (17)	−0.0101 (17)
C4	0.061 (3)	0.062 (3)	0.067 (3)	−0.024 (2)	0.010 (2)	−0.012 (2)
C5	0.052 (3)	0.060 (3)	0.097 (4)	−0.008 (2)	0.030 (3)	−0.024 (3)
C6	0.037 (2)	0.041 (2)	0.135 (4)	0.007 (2)	0.012 (3)	−0.007 (3)
C7	0.038 (2)	0.047 (2)	0.071 (2)	0.0017 (19)	0.0021 (19)	0.010 (2)
C8	0.0312 (17)	0.0319 (18)	0.050 (2)	−0.0033 (16)	−0.0032 (15)	−0.0037 (15)
C9	0.040 (2)	0.040 (2)	0.055 (2)	0.0005 (18)	−0.0045 (17)	−0.0031 (17)

Geometric parameters (Å, º) top

S—C3	1.773 (4)	C3—C4	1.391 (6)
S—C2	1.802 (5)	C3—C8	1.401 (5)
N—C9	1.330 (4)	C4—C5	1.382 (6)
N—C1	1.453 (4)	C4—H4A	0.9300
N—H0A	0.8600	C5—C6	1.354 (7)
O—C9	1.229 (4)	C5—H5A	0.9300
C1—C2	1.499 (6)	C6—C7	1.384 (6)
C1—H1A	0.9700	C6—H6A	0.9300
C1—H1B	0.9700	C7—C8	1.380 (5)
C2—H2A	0.9700	C7—H7A	0.9300
C2—H2B	0.9700	C8—C9	1.488 (5)

C3—S—C2	103.42 (19)	C5—C4—C3	120.8 (4)
C9—N—C1	124.5 (3)	C5—C4—H4A	119.6
C9—N—H0A	117.8	C3—C4—H4A	119.6
C1—N—H0A	117.8	C6—C5—C4	120.5 (4)
N—C1—C2	113.3 (3)	C6—C5—H5A	119.8
N—C1—H1A	108.9	C4—C5—H5A	119.8
C2—C1—H1A	108.9	C5—C6—C7	119.5 (4)
N—C1—H1B	108.9	C5—C6—H6A	120.2
C2—C1—H1B	108.9	C7—C6—H6A	120.2
H1A—C1—H1B	107.7	C8—C7—C6	121.6 (4)
C1—C2—S	114.1 (3)	C8—C7—H7A	119.2
C1—C2—H2A	108.7	C6—C7—H7A	119.2
S—C2—H2A	108.7	C7—C8—C3	118.8 (3)
C1—C2—H2B	108.7	C7—C8—C9	119.0 (3)
S—C2—H2B	108.7	C3—C8—C9	122.2 (3)
H2A—C2—H2B	107.6	O—C9—N	121.5 (4)
C4—C3—C8	118.8 (4)	O—C9—C8	119.5 (3)
C4—C3—S	118.6 (3)	N—C9—C8	118.9 (3)
C8—C3—S	122.1 (3)

C9—N—C1—C2	82.3 (5)	C6—C7—C8—C9	177.5 (4)
N—C1—C2—S	−49.9 (4)	C4—C3—C8—C7	0.8 (5)
C3—S—C2—C1	−29.6 (4)	S—C3—C8—C7	172.7 (3)
C2—S—C3—C4	−124.1 (3)	C4—C3—C8—C9	−176.4 (3)
C2—S—C3—C8	63.9 (3)	S—C3—C8—C9	−4.4 (5)
C8—C3—C4—C5	−1.4 (6)	C1—N—C9—O	176.3 (4)
S—C3—C4—C5	−173.6 (3)	C1—N—C9—C8	−2.7 (6)
C3—C4—C5—C6	1.0 (6)	C7—C8—C9—O	−45.4 (5)
C4—C5—C6—C7	0.1 (7)	C3—C8—C9—O	131.8 (4)
C5—C6—C7—C8	−0.7 (6)	C7—C8—C9—N	133.6 (4)
C6—C7—C8—C3	0.3 (6)	C3—C8—C9—N	−49.3 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···Oⁱ	0.86	2.05	2.824 (4)	149

Symmetry code: (i) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₉NOS
M_r	179.23
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	294
a, b, c (Å)	8.0510 (16), 8.9580 (18), 24.220 (5)
V (Å³)	1746.8 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.939, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	1704, 1704, 1089
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.166, 1.02
No. of reflections	1704
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.22

Computer programs: CAD-4 Software (Enraf–Nonius,1989), XCAD4 (Harms & Wocadlo,1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens,1996), SHELXL (Siemens,1996).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···Oⁱ	0.8600	2.0500	2.824 (4)	149.00

Symmetry code: (i) −x, y+1/2, −z+1/2.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University for support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–S19. CSD CrossRef Web of Science Google Scholar
Arya, V. P., Kaul, C. L., Grewal, R. S., David, J., Talwalker, P. K. & Shenoy, S. J. (1977). Indian J. Chem. B, 15, 720–726. CAS Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Version 5.0. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Ishibashi, H., Uegaki, M., Sakai, M. & Takeda, Y. (2001). Tetrahedron, 57, 2115–2120. Web of Science CrossRef CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Siemens (1996). SHELXTL. Version 5.06. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar