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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o113.
Published online 2007 December 6. doi:  10.1107/S1600536807062046
PMCID: PMC2915184

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

Abstract

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 [triangle]). For related literature, see: Ishibashi et al. (2001 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-64-0o113-scheme1.jpg

Experimental

Crystal data

  • C9H9NOS
  • M r = 179.23
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o113-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.062
  • wR(F 2) = 0.166
  • S = 1.02
  • 1704 reflections
  • 109 parameters
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.22 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062046/hk2393Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were positioned geometrically, with N—H = 0.86 Å (for NH) and C—H = 0.93 and 0.97 Å for aromatic and methylene H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N).

Figures

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.

Crystal data

C9H9NOSF000 = 752
Mr = 179.23Dx = 1.363 Mg m3
Orthorhombic, PbcaMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 25 reflections
a = 8.0510 (16) Åθ = 9–13º
b = 8.9580 (18) ŵ = 0.32 mm1
c = 24.220 (5) ÅT = 294 (2) K
V = 1746.8 (6) Å3Block, colorless
Z = 80.20 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.022
Radiation source: fine-focus sealed tubeθmax = 26.0º
Monochromator: graphiteθmin = 1.7º
T = 294(2) Kh = 0→9
ω/2θ scansk = 0→10
Absorption correction: ψ scan(North et al., 1968)l = 0→29
Tmin = 0.939, Tmax = 0.9693 standard reflections
1704 measured reflections every 120 min
1704 independent reflections intensity decay: none
1089 reflections with I > 2σ(I)

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.062H-atom parameters constrained
wR(F2) = 0.166  w = 1/[σ2(Fo2) + (0.060P)2 + 2.7P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
1704 reflectionsΔρmax = 0.23 e Å3
109 parametersΔρmin = −0.22 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
S0.20239 (14)0.28682 (12)0.17431 (4)0.0620 (4)
O−0.0306 (4)0.2669 (4)0.02305 (13)0.0753 (10)
N0.2218 (4)0.3438 (3)0.04867 (12)0.0452 (8)
H0A0.26510.29180.02250.054*
C10.3328 (4)0.4320 (4)0.08290 (17)0.0507 (10)
H1A0.28010.52690.09110.061*
H1B0.43360.45250.06230.061*
C20.3779 (5)0.3569 (5)0.1361 (2)0.0674 (13)
H2A0.43760.42750.15910.081*
H2B0.45240.27460.12820.081*
C30.0396 (4)0.4103 (4)0.15575 (16)0.0439 (9)
C4−0.0452 (5)0.4849 (5)0.19751 (19)0.0633 (12)
H4A−0.00850.47680.23380.076*
C5−0.1832 (6)0.5708 (5)0.1857 (2)0.0695 (13)
H5A−0.23750.62120.21400.083*
C6−0.2398 (5)0.5822 (5)0.1333 (2)0.0710 (14)
H6A−0.33270.64020.12550.085*
C7−0.1587 (4)0.5068 (4)0.09133 (18)0.0518 (10)
H7A−0.19880.51410.05540.062*
C8−0.0196 (4)0.4211 (4)0.10152 (14)0.0377 (8)
C90.0579 (4)0.3377 (4)0.05503 (16)0.0449 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S0.0642 (7)0.0529 (7)0.0691 (7)0.0009 (6)−0.0161 (5)0.0134 (5)
O0.0568 (18)0.088 (2)0.081 (2)−0.0102 (17)−0.0143 (16)−0.0395 (18)
N0.0378 (18)0.0425 (17)0.0553 (17)0.0002 (15)0.0038 (14)−0.0121 (14)
C10.0335 (19)0.040 (2)0.079 (3)−0.0057 (18)0.0068 (18)−0.014 (2)
C20.038 (2)0.059 (3)0.106 (4)0.001 (2)−0.013 (2)0.000 (3)
C30.0356 (19)0.0351 (19)0.061 (2)−0.0092 (17)0.0057 (17)−0.0101 (17)
C40.061 (3)0.062 (3)0.067 (3)−0.024 (2)0.010 (2)−0.012 (2)
C50.052 (3)0.060 (3)0.097 (4)−0.008 (2)0.030 (3)−0.024 (3)
C60.037 (2)0.041 (2)0.135 (4)0.007 (2)0.012 (3)−0.007 (3)
C70.038 (2)0.047 (2)0.071 (2)0.0017 (19)0.0021 (19)0.010 (2)
C80.0312 (17)0.0319 (18)0.050 (2)−0.0033 (16)−0.0032 (15)−0.0037 (15)
C90.040 (2)0.040 (2)0.055 (2)0.0005 (18)−0.0045 (17)−0.0031 (17)

Geometric parameters (Å, °)

S—C31.773 (4)C3—C41.391 (6)
S—C21.802 (5)C3—C81.401 (5)
N—C91.330 (4)C4—C51.382 (6)
N—C11.453 (4)C4—H4A0.9300
N—H0A0.8600C5—C61.354 (7)
O—C91.229 (4)C5—H5A0.9300
C1—C21.499 (6)C6—C71.384 (6)
C1—H1A0.9700C6—H6A0.9300
C1—H1B0.9700C7—C81.380 (5)
C2—H2A0.9700C7—H7A0.9300
C2—H2B0.9700C8—C91.488 (5)
C3—S—C2103.42 (19)C5—C4—C3120.8 (4)
C9—N—C1124.5 (3)C5—C4—H4A119.6
C9—N—H0A117.8C3—C4—H4A119.6
C1—N—H0A117.8C6—C5—C4120.5 (4)
N—C1—C2113.3 (3)C6—C5—H5A119.8
N—C1—H1A108.9C4—C5—H5A119.8
C2—C1—H1A108.9C5—C6—C7119.5 (4)
N—C1—H1B108.9C5—C6—H6A120.2
C2—C1—H1B108.9C7—C6—H6A120.2
H1A—C1—H1B107.7C8—C7—C6121.6 (4)
C1—C2—S114.1 (3)C8—C7—H7A119.2
C1—C2—H2A108.7C6—C7—H7A119.2
S—C2—H2A108.7C7—C8—C3118.8 (3)
C1—C2—H2B108.7C7—C8—C9119.0 (3)
S—C2—H2B108.7C3—C8—C9122.2 (3)
H2A—C2—H2B107.6O—C9—N121.5 (4)
C4—C3—C8118.8 (4)O—C9—C8119.5 (3)
C4—C3—S118.6 (3)N—C9—C8118.9 (3)
C8—C3—S122.1 (3)
C9—N—C1—C282.3 (5)C6—C7—C8—C9177.5 (4)
N—C1—C2—S−49.9 (4)C4—C3—C8—C70.8 (5)
C3—S—C2—C1−29.6 (4)S—C3—C8—C7172.7 (3)
C2—S—C3—C4−124.1 (3)C4—C3—C8—C9−176.4 (3)
C2—S—C3—C863.9 (3)S—C3—C8—C9−4.4 (5)
C8—C3—C4—C5−1.4 (6)C1—N—C9—O176.3 (4)
S—C3—C4—C5−173.6 (3)C1—N—C9—C8−2.7 (6)
C3—C4—C5—C61.0 (6)C7—C8—C9—O−45.4 (5)
C4—C5—C6—C70.1 (7)C3—C8—C9—O131.8 (4)
C5—C6—C7—C8−0.7 (6)C7—C8—C9—N133.6 (4)
C6—C7—C8—C30.3 (6)C3—C8—C9—N−49.3 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N—H0A···Oi0.862.052.824 (4)149

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2393).

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.
  • 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.
  • Enraf–Nonius (1989). CAD-4 Software Version 5.0. Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Ishibashi, H., Uegaki, M., Sakai, M. & Takeda, Y. (2001). Tetrahedron, 57, 2115–2120.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Siemens (1996). SHELXTL Version 5.06. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography