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The structure of the title compound, C18H17NO4S, has been established by an X-ray crystallographic study. The N and S atoms of the thia­zine ring are almost in the benzo plane, whereas the three C atoms are above the plane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801004846/cf6057sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801004846/cf6057Isup2.hkl
Contains datablock I

CCDC reference: 162831

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.001 Å
  • R factor = 0.045
  • wR factor = 0.048
  • Data-to-parameter ratio = 11.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_731 Alert C Bond Calc 1.4185(9), Rep 1.4184(4) .... 2.25 s.u-Ratio O18 -C3 1.555 1.555 PLAT_731 Alert C Bond Calc 1.4482(17), Rep 1.4482(5) .... 3.40 s.u-Ratio O23 -C24 1.555 1.555 PLAT_731 Alert C Bond Calc 1.5449(14), Rep 1.5450(5) .... 2.80 s.u-Ratio C2 -C3 1.555 1.555 PLAT_731 Alert C Bond Calc 1.3928(14), Rep 1.3929(5) .... 2.80 s.u-Ratio C6 -C11 1.555 1.555 PLAT_731 Alert C Bond Calc 1.381(2), Rep 1.3809(7) .... 2.86 s.u-Ratio C8 -C9 1.555 1.555 PLAT_731 Alert C Bond Calc 1.5122(15), Rep 1.5121(6) .... 2.50 s.u-Ratio C20 -C21 1.555 1.555 PLAT_732 Alert C Angle Calc 112.89(8), Rep 112.89(3) .... 2.67 s.u-Ratio C3 -C2 -C12 1.555 1.555 1.555 PLAT_732 Alert C Angle Calc 107.81(7), Rep 107.82(3) .... 2.33 s.u-Ratio O18 -C3 -C4 1.555 1.555 1.555 PLAT_732 Alert C Angle Calc 119.01(9), Rep 119.01(4) .... 2.25 s.u-Ratio N5 -C6 -C7 1.555 1.555 1.555 PLAT_732 Alert C Angle Calc 120.15(10), Rep 120.15(4) .... 2.50 s.u-Ratio C6 -C7 -C8 1.555 1.555 1.555 PLAT_732 Alert C Angle Calc 120.35(10), Rep 120.35(4) .... 2.50 s.u-Ratio C8 -C9 -C10 1.555 1.555 1.555 PLAT_732 Alert C Angle Calc 120.56(11), Rep 120.56(4) .... 2.75 s.u-Ratio C9 -C10 -C11 1.555 1.555 1.555 PLAT_732 Alert C Angle Calc 118.48(8), Rep 118.47(3) .... 2.67 s.u-Ratio S1 -C11 -C10 1.555 1.555 1.555 PLAT_732 Alert C Angle Calc 125.12(10), Rep 125.12(4) .... 2.50 s.u-Ratio O22 -C21 -O23 1.555 1.555 1.555
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
14 Alert Level C = Please check

Comment top

A number of 1,5-benzothiazepine derivatives have been shown to exhibit pharmacological propeties as calcium antagonists (Akiyoshi et al., 1992), coronary vasodilators (Hirozumi et al., 1991), antihypertensives (Hiroshi et al., 1992) and blood-platelet aggregation inhibitors (Hirozumi et al., 1990). The success of this class of products has stimulated significant activity in related chemical synthesis, directed at the synthesis of both analogous and enantiomerically pure compounds.

The thiazepine ring in the title compound, (I), is fused with the benzo ring and has four substituents: phenyl in position 2, hydroxy in position 3, oxo in position 4 and acetate in position 5. The seven-membered ring contains a planar N5—C6—C11—S1 fragment (r.m.s. deviation: 0.014 Å), almost coplanar with the adjacent benzo ring [angle 5.3 (3)°]. The three other atoms of the benzothiazepine system (C2, C3 and C4) are on the same side of the N5—C6—C11—S1 fragment.

Experimental top

A mixture of 2-aminothiophenol (110 mmol, 13.75 g) with ethyl 3-phenylglycidate (110 mmol, 21.12 g) was heated with stirring at 393 K for 1 h under a nitrogen atmosphere and then at 433 K for 16 h. The cooled mixture was dissolved in ethanol (30 ml) and allowed to stand at 278 K overnight. The precipitated needles were filtered off, washed with ethanol and recrystallized from ethanol to give 7.4 g (25%) of 3-hydroxy-2-phenyl-1,5-benzothiazepin-4(5H)-one. To a solution of this compound (5 mmol, 1.36 g) in acetone (40 ml) was added K2CO3 (20 mmol, 2.76 g) and methyl chloroacetate (40 mmol, 4.34 g). The mixture was refluxed and the reaction was monitored by thin-layer chromatography (ether/CHCl3). After filtration, the solvent was evaporated in vacuo to give 1.20 g (70%) of methyl (3-hydroxy-4-oxo-2-phenyl-1,5-benzothiazepin-5-yl) acetate, (I), m.p. 429 K. Analysis calculated for C18H17NO2S: C 62.96, H 4.99, N 4.08%; found C 62.88, H 5.10, N 4.21%. Mass FAB+ (NBA): 344 (M + 1).

Computing details top

Data collection: KappaCCD Reference Manual (Nonius, 1998); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: maXus (Mackay et al., 1999); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: maXus.

Figures top
[Figure 1] Fig. 1. Perspective view of the title molecule showing the labelling of the atoms, with displacement ellipsoids at the 50% probability level.
(I) top
Crystal data top
C18H17NO4SF(000) = 720
Mr = 343.40Dx = 1.416 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 13.6308 (8) ÅCell parameters from 10319 reflections
b = 15.1336 (9) Åθ = 1–26.4°
c = 16.154 (1) ŵ = 0.22 mm1
β = 151.086 (3)°T = 298 K
V = 1611.2 (2) Å3Prism, violet
Z = 40.40 × 0.30 × 0.20 mm
Data collection top
KappaCCD
diffractometer
Rint = 0.046
Radiation source: fine-focus sealed tubeθmax = 26.4°
ϕ scansh = 1616
3302 measured reflectionsk = 180
3156 independent reflectionsl = 2016
2569 reflections with I > 3σ(I)
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: geom, diff
R[F2 > 2σ(F2)] = 0.045H-atom parameters not refined
wR(F2) = 0.048Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo2) + 0.03Fo2]
S = 1.51(Δ/σ)max = 0.015
2569 reflectionsΔρmax = 0.24 e Å3
217 parametersΔρmin = 0.30 e Å3
Primary atom site location: structure-invariant direct methods
Crystal data top
C18H17NO4SV = 1611.2 (2) Å3
Mr = 343.40Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.6308 (8) ŵ = 0.22 mm1
b = 15.1336 (9) ÅT = 298 K
c = 16.154 (1) Å0.40 × 0.30 × 0.20 mm
β = 151.086 (3)°
Data collection top
KappaCCD
diffractometer
2569 reflections with I > 3σ(I)
3302 measured reflectionsRint = 0.046
3156 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.045217 parameters
wR(F2) = 0.048H-atom parameters not refined
S = 1.51Δρmax = 0.24 e Å3
2569 reflectionsΔρmin = 0.30 e Å3
Special details top

Geometry. All standard uncertainties (except dihedral angles between l.s. planes) are estimated using the full covariance matrix. The standard uncertainties in cell dimensions are are used in calculating the standard uncertainties of bond distances, angles and torsion angles. Angles between l.s. planes have standard uncertainties calculated from atomic positional standard uncertainties; the errors in cell dimensions are not used in this case.

Refinement. Refinement on F2

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.043323 (18)0.376328 (8)0.016113 (15)0.09284 (7)
O180.01596 (4)0.32975 (2)0.30649 (4)0.08259 (17)
O190.29436 (5)0.43419 (2)0.05234 (4)0.09537 (18)
O220.67789 (5)0.30762 (2)0.20966 (4)0.1256 (2)
O230.84397 (5)0.43524 (2)0.34720 (4)0.1122 (2)
N50.41618 (5)0.35605 (2)0.14507 (4)0.06322 (19)
C20.07943 (6)0.36288 (3)0.20796 (5)0.0685 (2)
C30.07045 (6)0.32628 (3)0.16231 (5)0.0662 (2)
C40.26885 (6)0.37712 (3)0.01795 (5)0.0697 (2)
C60.39450 (6)0.29014 (3)0.19221 (5)0.0694 (2)
C70.54413 (7)0.22635 (3)0.31138 (6)0.0874 (3)
C80.53301 (8)0.16520 (3)0.36676 (6)0.1089 (3)
C90.37105 (9)0.16700 (3)0.30134 (7)0.1261 (3)
C100.21874 (7)0.22834 (3)0.17918 (6)0.1045 (3)
C110.22828 (6)0.29122 (3)0.12267 (5)0.0748 (2)
C120.17461 (6)0.44937 (3)0.30402 (5)0.0689 (2)
C130.08121 (7)0.53048 (3)0.22189 (6)0.0922 (3)
C140.17508 (9)0.60806 (3)0.31654 (8)0.1468 (3)
C150.36056 (9)0.60541 (4)0.49229 (8)0.1517 (4)
C160.45319 (7)0.52573 (4)0.57519 (6)0.1052 (3)
C170.36203 (6)0.44790 (3)0.48200 (6)0.0810 (3)
C200.61013 (6)0.40095 (3)0.27691 (5)0.0745 (2)
C210.71033 (6)0.37427 (3)0.27050 (5)0.0656 (2)
C240.95452 (8)0.41952 (3)0.35279 (7)0.1240 (3)
H20.186630.320260.282220.05276*
H30.097930.265650.128600.05190*
H70.655200.224640.355000.06208*
H80.638680.122100.451400.07114*
H90.362770.124970.339610.07850*
H100.105400.228510.132810.07015*
H130.049190.532960.099170.06338*
H140.110360.663960.259390.08474*
H150.426400.659040.557830.09155*
H160.581800.523580.698030.07708*
H170.427490.392170.539980.06170*
H180.049860.387580.286240.06267*
H20A0.698350.385570.387110.05748*
H20B0.588020.463650.260430.05748*
H24A1.046420.467500.410720.08136*
H24B0.860420.415020.238100.08136*
H24C1.029720.365400.413020.08136*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.04872 (7)0.04516 (7)0.04300 (7)0.00509 (6)0.04246 (7)0.00202 (6)
O180.04275 (18)0.0538 (2)0.03141 (17)0.00596 (15)0.03293 (16)0.00048 (14)
O190.04561 (19)0.04791 (19)0.04614 (19)0.00379 (15)0.04120 (18)0.00991 (15)
O220.0573 (2)0.0458 (2)0.0696 (2)0.00760 (17)0.0565 (2)0.01519 (18)
O230.0495 (2)0.0456 (2)0.0631 (2)0.01029 (16)0.0509 (2)0.01049 (17)
N50.02961 (19)0.0412 (2)0.02628 (19)0.00350 (15)0.02420 (18)0.00141 (15)
C20.0335 (2)0.0326 (2)0.0329 (2)0.00331 (18)0.0297 (2)0.00450 (18)
C30.0343 (2)0.0335 (2)0.0288 (2)0.00331 (18)0.0279 (2)0.00090 (18)
C40.0338 (2)0.0346 (2)0.0340 (2)0.00502 (19)0.0309 (2)0.00359 (19)
C60.0387 (2)0.0336 (2)0.0277 (2)0.00261 (19)0.0292 (2)0.00270 (18)
C70.0434 (3)0.0486 (3)0.0361 (3)0.0060 (2)0.0338 (3)0.0060 (2)
C80.0613 (3)0.0502 (3)0.0411 (3)0.0117 (3)0.0431 (3)0.0134 (2)
C90.0744 (4)0.0492 (3)0.0514 (3)0.0061 (3)0.0558 (3)0.0029 (3)
C100.0580 (3)0.0466 (3)0.0460 (3)0.0086 (2)0.0475 (3)0.0050 (2)
C110.0404 (3)0.0353 (2)0.0324 (2)0.0042 (2)0.0326 (2)0.00441 (19)
C120.0322 (2)0.0336 (2)0.0354 (2)0.00140 (19)0.0310 (2)0.00038 (19)
C130.0468 (3)0.0372 (3)0.0462 (3)0.0000 (2)0.0424 (3)0.0002 (2)
C140.0792 (4)0.0359 (3)0.0813 (4)0.0035 (3)0.0753 (4)0.0039 (3)
C150.0791 (4)0.0572 (4)0.0790 (4)0.0314 (3)0.0744 (4)0.0326 (3)
C160.0472 (3)0.0783 (4)0.0441 (3)0.0229 (3)0.0410 (3)0.0200 (3)
C170.0364 (3)0.0512 (3)0.0375 (3)0.0035 (2)0.0331 (3)0.0002 (2)
C200.0339 (2)0.0454 (3)0.0330 (3)0.0064 (2)0.0288 (2)0.0070 (2)
C210.0295 (2)0.0366 (2)0.0296 (2)0.0014 (2)0.0248 (2)0.0017 (2)
C240.0546 (3)0.0633 (3)0.0663 (4)0.0043 (3)0.0556 (3)0.0085 (3)
Geometric parameters (Å, º) top
S1—C21.8350 (4)C6—C71.3870 (6)
S1—C111.7738 (4)C6—C111.3929 (5)
O18—C31.4184 (4)C7—C81.3847 (7)
O19—C41.2304 (5)C8—C91.3809 (7)
O22—C211.1908 (5)C9—C101.3761 (7)
O23—C211.3243 (5)C10—C111.4013 (6)
O23—C241.4482 (5)C12—C131.3896 (6)
N5—C41.3457 (5)C12—C171.3908 (6)
N5—C61.4339 (5)C13—C141.3887 (6)
N5—C201.4594 (5)C14—C151.3739 (7)
C2—C31.5450 (5)C15—C161.3718 (8)
C2—C121.5098 (6)C16—C171.3867 (7)
C3—C41.5176 (6)C20—C211.5121 (6)
C2—S1—C11103.89 (2)C7—C8—C9119.88 (5)
C21—O23—C24116.62 (4)C8—C9—C10120.35 (4)
C4—N5—C6123.77 (4)C9—C10—C11120.56 (4)
C4—N5—C20116.07 (3)S1—C11—C6122.47 (3)
C6—N5—C20120.07 (3)S1—C11—C10118.47 (3)
S1—C2—C3111.33 (3)C6—C11—C10118.67 (4)
S1—C2—C12109.42 (3)C2—C12—C13122.66 (4)
C3—C2—C12112.89 (3)C2—C12—C17118.80 (4)
O18—C3—C2110.64 (3)C13—C12—C17118.53 (4)
O18—C3—C4107.82 (3)C12—C13—C14120.30 (4)
C2—C3—C4112.63 (3)C13—C14—C15120.39 (5)
O19—C4—N5121.50 (4)C14—C15—C16119.95 (5)
O19—C4—C3119.33 (4)C15—C16—C17120.17 (5)
N5—C4—C3119.11 (3)C12—C17—C16120.64 (5)
N5—C6—C7119.01 (4)N5—C20—C21111.51 (3)
N5—C6—C11120.63 (4)O22—C21—O23125.12 (4)
C7—C6—C11120.34 (4)O22—C21—C20125.28 (4)
C6—C7—C8120.15 (4)O23—C21—C20109.57 (4)

Experimental details

Crystal data
Chemical formulaC18H17NO4S
Mr343.40
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)13.6308 (8), 15.1336 (9), 16.154 (1)
β (°) 151.086 (3)
V3)1611.2 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.22
Crystal size (mm)0.40 × 0.30 × 0.20
Data collection
DiffractometerKappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 3σ(I)] reflections
3302, 3156, 2569
Rint0.046
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.048, 1.51
No. of reflections2569
No. of parameters217
No. of restraints?
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.24, 0.30

Computer programs: KappaCCD Reference Manual (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), maXus (Mackay et al., 1999), ORTEPII (Johnson, 1976), maXus.

 

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