1,6,6-Trimethyl-1H-chromeno[6,7-d]thia­zol-2(6H)-one

Tang, J.; Wang, Y.; Zhang, B.-N.; Xia, P.

doi:10.1107/S1600536808010623

organic compounds

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Volume 64| Part 5| May 2008| Page o891

doi:10.1107/S1600536808010623

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1,6,6-Trimethyl-1H-chromeno[6,7-d]thiazol-2(6H)-one

Jian Tang,^a Yang Wang,^a Bei-Na Zhang ^a and Peng Xia ^a ^*

^aDepartment of Medicinal Chemistry, School of Pharmacy, Fudan University, Shanghai 200032, People's Republic of China
^*Correspondence e-mail: pxia@fudan.edu.cn

(Received 10 March 2008; accepted 17 April 2008; online 23 April 2008)

The title compound, C₁₃H₁₃NO₂S, was prepared by a thermocyclization reaction from 3-methyl-6-(2-methylbut-3-yn-2-yloxy)benzo[d]thiazol-2(3H)-one. In the crystal structure, the methylthiazole unit is planar, while the pyran ring assumes a screw-boat conformation. Intramolecular C—H⋯O hydrogen bonding helps to stabilize the molecular structure.

Related literature

For general background, see: Gunatilaka et al. (1994 ); Ucar et al. (1998 ). For details of the synthesis, see: Delhomel et al. (2001 ).

Experimental

Crystal data

C₁₃H₁₃NO₂S
M_r = 247.30
Triclinic, $[P \overline 1]$
a = 7.376 (2) Å
b = 8.395 (2) Å
c = 10.536 (2) Å
α = 106.13 (2)°
β = 98.16 (2)°
γ = 94.08 (2)°
V = 616.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 298 (2) K
0.20 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2765 measured reflections
2207 independent reflections
1387 reflections with I > 2σ(I)
R_int = 0.023
3 standard reflections frequency: 60 min intensity decay: 0.5%

Refinement

R[F² > 2σ(F²)] = 0.076
wR(F²) = 0.216
S = 1.05
2207 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 0.91 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1ⁱ	0.93	2.56	3.331 (5)	140
Symmetry code: (i) x, y+1, z+1.

Data collection: CAD-4 Software (Enraf–Nonius, 1984 ); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808010623/xu2407sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808010623/xu2407Isup2.hkl

checkCIF report

Comment top

2,2-Dimethyl-2H-benzopyran fused thiazolone is a novel potential bioactive core (Gunatilaka et al. 1994; Ucar et al. 1998). As part of our research program on new antitumor and antiviral agents based on bioisosterism, we synthesized the title compound and report here its crystal structure (Fig. 1).

The compound is a three rings-fused heterocycle compound. The methyl thiazole moiety shows a planar structure. The pyran ring assumes a screw-boat conformation. The C6–C7 bond distance of 1.312 (5) Å indicates a typical C═C double bond. Intramolecular C—H···O hydrogen bonding helps to stabilize the crystal structure (Table 1 and Fig. 2).

Related literature top

For general background, see: Gunatilaka et al. (1994); Ucar et al. (1998). For details of the synthesis, see: Delhomel et al. (2001).

Experimental top

The title compound was synthesized by the thermo-cyclization reaction of 3-methyl-6-(2-methylbut-3-yn-2-yloxy)benzo[d]thiazol-2(3H)-one. A mixture of 6-hydroxy-3-methyl-2(3H)-benzothiazolone (508 mg, 2.6 mmol) (Delhomel et al. 2001), 3-methyl-3-chloro-but-1-yne (320 mg, 3.12 mmol) and K₂CO₃ (1.43 g, 10.4 mmol) was stirred in acetone (30 ml) for 5 h under reflux condition, then filtered and removed the solvent. To the residue was added N,N-diethylaniline (5 ml) and further refluxed for 2 h. The resulting solution was poured to ice water (100 ml) and extracted with acetyl acetate, and the organic layer was dried over Na₂SO₄, filtered, and concentrated under reduced pressure. The residue was isolated by chromatography on silica gel column with petroleum ether/EtOAc (18/1) as eluent to afford the pure compound. The solid was collected and recrystallized from acetyl acetate to give colorless crystals which were available for the single-crystal X-ray diffraction analysis. Yield: 33.5%.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1984); cell refinement: CAD-4 Software (Enraf–Nonius, 1984); data reduction: XCAD, PSI and EAC (Enraf–Nonius, 1984); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of (I), viewed down the c axis, showing one demensional supra-molecular chain connected by C—H···Oⁱ hydrogen bonding [symmetry code: (i) = x, y + 1, z + 1). H atoms not involved in hydrogen bonding have been omitted.

1,6,6-Trimethyl-6H-chromeno[6,7-d]thiazol-2(3H)-one top

Crystal data top

C₁₃H₁₃NO₂S	Z = 2
M_r = 247.30	F(000) = 260
Triclinic, P1	D_x = 1.333 Mg m⁻³
Hall symbol: -P 1	Melting point = 376–378 K
a = 7.376 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.395 (2) Å	Cell parameters from 25 reflections
c = 10.536 (2) Å	θ = 10.2–13.7°
α = 106.13 (2)°	µ = 0.25 mm⁻¹
β = 98.16 (2)°	T = 298 K
γ = 94.08 (2)°	Parallelepiped, colourless
V = 616.2 (3) Å³	0.20 × 0.20 × 0.20 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.023
Radiation source: fine-focus sealed tube	θ_max = 25.2°, θ_min = 2.0°
Graphite monochromator	h = −1→8
ω/2θ scans	k = −10→10
2765 measured reflections	l = −12→12
2207 independent reflections	3 standard reflections every 60 min
1387 reflections with I > 2σ(I)	intensity decay: 0.5%

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.216	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.1546P)²] where P = (F_o² + 2F_c²)/3
2207 reflections	(Δ/σ)_max < 0.001
157 parameters	Δρ_max = 0.91 e Å⁻³
0 restraints	Δρ_min = −0.68 e Å⁻³

Crystal data top

C₁₃H₁₃NO₂S	γ = 94.08 (2)°
M_r = 247.30	V = 616.2 (3) Å³
Triclinic, P1	Z = 2
a = 7.376 (2) Å	Mo Kα radiation
b = 8.395 (2) Å	µ = 0.25 mm⁻¹
c = 10.536 (2) Å	T = 298 K
α = 106.13 (2)°	0.20 × 0.20 × 0.20 mm
β = 98.16 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.023
2765 measured reflections	3 standard reflections every 60 min
2207 independent reflections	intensity decay: 0.5%
1387 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.076	0 restraints
wR(F²) = 0.216	H-atom parameters constrained
S = 1.05	Δρ_max = 0.91 e Å⁻³
2207 reflections	Δρ_min = −0.68 e Å⁻³
157 parameters

Special details top

Experimental. ¹H NMR (CDCl_3,400 MHz): δ 6.87 (s, 1H, 9-H); 6.64 (s, 1H, 4-H); 6.35 (1H, d, J = 9.78 Hz, 8-H); 5.68 (d, 1H, J = 9.78 Hz, 7-H); 3.40 (s, 3H, 1-CH₃); 1.43 (s, 6H, 6-CH₃). MS: m/z (%) 247 (M⁺, 22.17).

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
S1	0.72819 (14)	0.52182 (13)	−0.25523 (9)	0.0529 (4)
N1	0.7791 (4)	0.3420 (4)	−0.0937 (3)	0.0438 (7)
O1	0.8000 (4)	0.2061 (4)	−0.3119 (3)	0.0670 (9)
O2	0.6410 (4)	0.9748 (3)	0.1700 (2)	0.0456 (7)
C1	0.7748 (5)	0.3288 (5)	−0.2252 (4)	0.0510 (10)
C2	0.8103 (5)	0.2021 (5)	−0.0421 (4)	0.0572 (11)
H2A	0.8403	0.1115	−0.1114	0.086*
H2B	0.7008	0.1671	−0.0128	0.086*
H2C	0.9105	0.2348	0.0321	0.086*
C3	0.7480 (4)	0.4981 (4)	−0.0139 (3)	0.0383 (8)
C4	0.7478 (4)	0.5454 (4)	0.1217 (4)	0.0410 (8)
H4	0.7695	0.4696	0.1703	0.049*
C5	0.7150 (4)	0.7070 (4)	0.1869 (3)	0.0384 (8)
C6	0.7087 (5)	0.7649 (5)	0.3289 (4)	0.0471 (9)
H6	0.7087	0.6891	0.3786	0.056*
C7	0.7028 (5)	0.9237 (5)	0.3877 (4)	0.0509 (10)
H7	0.6938	0.9579	0.4782	0.061*
C8	0.7103 (5)	1.0517 (4)	0.3131 (3)	0.0454 (9)
C9	0.9067 (6)	1.1285 (5)	0.3310 (4)	0.0629 (12)
H9A	0.9809	1.0437	0.2938	0.094*
H9B	0.9534	1.1774	0.4248	0.094*
H9C	0.9108	1.2132	0.2860	0.094*
C10	0.5804 (6)	1.1829 (6)	0.3549 (4)	0.0661 (13)
H10A	0.5912	1.2639	0.3068	0.099*
H10B	0.6126	1.2374	0.4494	0.099*
H10C	0.4558	1.1301	0.3349	0.099*
C11	0.6830 (4)	0.8184 (4)	0.1118 (3)	0.0376 (8)
C12	0.6816 (5)	0.7719 (4)	−0.0248 (3)	0.0403 (8)
H12	0.6586	0.8470	−0.0739	0.048*
C13	0.7152 (5)	0.6107 (4)	−0.0871 (3)	0.0407 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0508 (6)	0.0578 (7)	0.0427 (6)	0.0037 (4)	0.0053 (4)	0.0046 (4)
N1	0.0257 (14)	0.0416 (17)	0.0569 (18)	0.0002 (12)	0.0024 (12)	0.0056 (14)
O1	0.0605 (19)	0.0622 (19)	0.0608 (18)	0.0140 (15)	0.0033 (14)	−0.0090 (15)
O2	0.0475 (15)	0.0445 (14)	0.0390 (13)	0.0094 (11)	−0.0031 (10)	0.0073 (11)
C1	0.0264 (18)	0.058 (2)	0.052 (2)	−0.0016 (16)	−0.0012 (15)	−0.0037 (18)
C2	0.032 (2)	0.050 (2)	0.082 (3)	0.0036 (17)	0.0020 (19)	0.012 (2)
C3	0.0212 (15)	0.0409 (19)	0.0482 (19)	−0.0024 (13)	0.0028 (13)	0.0083 (16)
C4	0.0258 (17)	0.046 (2)	0.050 (2)	−0.0022 (14)	−0.0010 (14)	0.0166 (17)
C5	0.0239 (16)	0.048 (2)	0.0385 (18)	−0.0033 (14)	−0.0017 (13)	0.0108 (15)
C6	0.042 (2)	0.054 (2)	0.045 (2)	0.0060 (16)	0.0023 (16)	0.0151 (17)
C7	0.047 (2)	0.065 (3)	0.0359 (18)	0.0069 (18)	−0.0001 (16)	0.0098 (18)
C8	0.041 (2)	0.049 (2)	0.0383 (19)	0.0072 (16)	−0.0015 (15)	0.0032 (16)
C9	0.046 (2)	0.066 (3)	0.067 (3)	−0.006 (2)	−0.005 (2)	0.013 (2)
C10	0.068 (3)	0.072 (3)	0.049 (2)	0.029 (2)	0.000 (2)	0.003 (2)
C11	0.0227 (16)	0.0403 (19)	0.0435 (18)	−0.0010 (13)	−0.0011 (13)	0.0065 (15)
C12	0.0338 (18)	0.044 (2)	0.0393 (18)	−0.0031 (14)	−0.0026 (14)	0.0121 (15)
C13	0.0298 (17)	0.044 (2)	0.0401 (18)	−0.0064 (14)	−0.0014 (13)	0.0060 (15)

Geometric parameters (Å, º) top

S1—C13	1.740 (4)	C5—C6	1.447 (5)
S1—C1	1.783 (4)	C6—C7	1.312 (5)
N1—C1	1.354 (5)	C6—H6	0.9300
N1—C3	1.401 (4)	C7—C8	1.500 (5)
N1—C2	1.444 (5)	C7—H7	0.9300
O1—C1	1.218 (4)	C8—C9	1.507 (5)
O2—C11	1.364 (4)	C8—C10	1.525 (5)
O2—C8	1.464 (4)	C9—H9A	0.9599
C2—H2A	0.9599	C9—H9B	0.9599
C2—H2B	0.9599	C9—H9C	0.9599
C2—H2C	0.9599	C10—H10A	0.9599
C3—C4	1.373 (5)	C10—H10B	0.9599
C3—C13	1.389 (5)	C10—H10C	0.9599
C4—C5	1.395 (5)	C11—C12	1.381 (5)
C4—H4	0.9300	C12—C13	1.388 (5)
C5—C11	1.395 (5)	C12—H12	0.9300

C13—S1—C1	91.10 (17)	C8—C7—H7	119.1
C1—N1—C3	115.4 (3)	O2—C8—C7	110.5 (3)
C1—N1—C2	121.4 (3)	O2—C8—C9	109.2 (3)
C3—N1—C2	123.2 (3)	C7—C8—C9	109.5 (3)
C11—O2—C8	118.1 (3)	O2—C8—C10	103.6 (3)
O1—C1—N1	126.6 (4)	C7—C8—C10	111.9 (3)
O1—C1—S1	123.7 (3)	C9—C8—C10	112.1 (3)
N1—C1—S1	109.8 (3)	C8—C9—H9A	109.5
N1—C2—H2A	109.5	C8—C9—H9B	109.5
N1—C2—H2B	109.5	H9A—C9—H9B	109.5
H2A—C2—H2B	109.5	C8—C9—H9C	109.5
N1—C2—H2C	109.5	H9A—C9—H9C	109.5
H2A—C2—H2C	109.5	H9B—C9—H9C	109.5
H2B—C2—H2C	109.5	C8—C10—H10A	109.5
C4—C3—C13	120.2 (3)	C8—C10—H10B	109.5
C4—C3—N1	127.2 (3)	H10A—C10—H10B	109.5
C13—C3—N1	112.6 (3)	C8—C10—H10C	109.5
C3—C4—C5	120.2 (3)	H10A—C10—H10C	109.5
C3—C4—H4	119.9	H10B—C10—H10C	109.5
C5—C4—H4	119.9	O2—C11—C12	117.5 (3)
C11—C5—C4	118.8 (3)	O2—C11—C5	120.8 (3)
C11—C5—C6	117.9 (3)	C12—C11—C5	121.6 (3)
C4—C5—C6	123.4 (3)	C11—C12—C13	118.4 (3)
C7—C6—C5	120.3 (4)	C11—C12—H12	120.8
C7—C6—H6	119.8	C13—C12—H12	120.8
C5—C6—H6	119.8	C12—C13—C3	120.8 (3)
C6—C7—C8	121.8 (3)	C12—C13—S1	128.0 (3)
C6—C7—H7	119.1	C3—C13—S1	111.2 (3)

C3—N1—C1—O1	179.1 (3)	C6—C7—C8—O2	25.8 (5)
C2—N1—C1—O1	−2.0 (5)	C6—C7—C8—C9	−94.5 (4)
C3—N1—C1—S1	−0.2 (3)	C6—C7—C8—C10	140.6 (4)
C2—N1—C1—S1	178.6 (2)	C8—O2—C11—C12	−155.9 (3)
C13—S1—C1—O1	−179.8 (3)	C8—O2—C11—C5	27.9 (4)
C13—S1—C1—N1	−0.4 (2)	C4—C5—C11—O2	176.6 (3)
C1—N1—C3—C4	−178.9 (3)	C6—C5—C11—O2	−2.2 (5)
C2—N1—C3—C4	2.2 (5)	C4—C5—C11—C12	0.5 (5)
C1—N1—C3—C13	1.0 (4)	C6—C5—C11—C12	−178.2 (3)
C2—N1—C3—C13	−177.9 (3)	O2—C11—C12—C13	−176.9 (3)
C13—C3—C4—C5	−0.2 (5)	C5—C11—C12—C13	−0.8 (5)
N1—C3—C4—C5	179.7 (3)	C11—C12—C13—C3	0.5 (5)
C3—C4—C5—C11	−0.1 (5)	C11—C12—C13—S1	−177.9 (3)
C3—C4—C5—C6	178.6 (3)	C4—C3—C13—C12	0.0 (5)
C11—C5—C6—C7	−10.8 (5)	N1—C3—C13—C12	−180.0 (3)
C4—C5—C6—C7	170.5 (3)	C4—C3—C13—S1	178.7 (2)
C5—C6—C7—C8	−2.6 (5)	N1—C3—C13—S1	−1.3 (3)
C11—O2—C8—C7	−37.9 (4)	C1—S1—C13—C12	179.5 (3)
C11—O2—C8—C9	82.5 (4)	C1—S1—C13—C3	1.0 (2)
C11—O2—C8—C10	−157.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.93	2.56	3.331 (5)	140

Symmetry code: (i) x, y+1, z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃NO₂S
M_r	247.30
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.376 (2), 8.395 (2), 10.536 (2)
α, β, γ (°)	106.13 (2), 98.16 (2), 94.08 (2)
V (Å³)	616.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2765, 2207, 1387
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.076, 0.216, 1.05
No. of reflections	2207
No. of parameters	157
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.91, −0.68

Computer programs: CAD-4 Software (Enraf–Nonius, 1984), XCAD, PSI and EAC (Enraf–Nonius, 1984), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.93	2.56	3.331 (5)	140.4

Symmetry code: (i) x, y+1, z+1.

References

Delhomel, J. F., Yous, S., Depreux, P. & Lesieur, D. (2001). J. Heterocycl. Chem. 38, 633–639. CrossRef CAS Google Scholar
Enraf–Nonius (1984). CAD-4 Software. Enraf-Nonius, Delft, The Netherlands. Google Scholar
Gunatilaka, L., Kingston, D., Wijeratne, K., Bandara, R., Hofmann, G. & Johnson, R. (1994). J. Nat. Prod. 57, 518–520. CrossRef CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ucar, H., Van derpoorten, K., Cacciaguerra, S., Spampinato, S., Stables, J. P., Depovere, P., Isa, M., Masereel, B., Delarge, J. & Poupaert, J. H. (1998). J. Med. Chem. 41, 1138–1145. Web of Science CrossRef CAS PubMed Google Scholar

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doi:10.1107/S1600536808010623

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