4-(5-Oxo-5H-1,2,4-dithia­zol-3-yl)phenyl 4-methyl­benzene­sulfonate

Yang, J.-Z.; Pi, W.-Y.; Luo, Y.-F.

doi:10.1107/S1600536811055607

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o450

doi:10.1107/S1600536811055607

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4-(5-Oxo-5H-1,2,4-dithiazol-3-yl)phenyl 4-methylbenzenesulfonate

Jian-Zhong Yang,^a Wei-Yi Pi ^a and You-Fu Luo ^a ^*

^aState Key Laboratory of Biotherapy, West China Hospital, Sichuan University, Chengdu 610041, People's Republic of China
^*Correspondence e-mail: luo_youfu@scu.edu.cn

(Received 12 December 2011; accepted 25 December 2011; online 18 January 2012)

In the molecular structure of the title compound, C₁₅H₁₁NO₄S₃, the 1,2,4-dithiazolone and central benzene rings are approximately coplanar, making a dihedral angle of 3.08 (7)°. The central benzene ring and the 4-methylbenzene ring subtend a dihedral angle of 57.47 (8)°. In the crystal, π–π stacking occurs between the central benzene ring and the 1,2,4-dithiazolone ring of adjacent molecules, which are aligned almost parallel, the centroid–centroid distance being 3.555 (7) Å.

Related literature

For the synthesis of related compounds, see: Cho et al. (2003 ); Chen et al. (1996 ). For their biological activity, see: Iwakawa et al. (1994 ).

Experimental

Crystal data

C₁₅H₁₁NO₄S₃
M_r = 365.43
Orthorhombic, P b c n
a = 30.2449 (9) Å
b = 7.0841 (3) Å
c = 14.6755 (5) Å
V = 3144.36 (18) Å³
Z = 8
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 145 K
0.25 × 0.20 × 0.20 mm

Data collection

Agilent Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.952, T_max = 1.000
6725 measured reflections
2775 independent reflections
2355 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.078
S = 1.04
2775 reflections
209 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811055607/im2348sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811055607/im2348Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811055607/im2348Isup3.cml

checkCIF report

Comment top

3H-1,2,4-dithiazol-3-one derivatives have been reported to posses antibacterial activity against a variety of bacteria and fungus strains including Staphylococcus aureus, Pasteurella piscicida and Botlytis cinerea (Iwakawa et al., 1994).

The molecular structure of the title compound is shown in Fig. 1. The central benzene ring is twisted away from the planes of the 3H-1,2,4-dithiazol-3-one and 4-methylbenzene rings by 3.08 (7) and 57.47 (8)°, respectively. In the crystal structure, intermolecular π-π stacking between central benzene rings and 3H-1,2,4-dithiazol-3-one rings of adjacent molecules which are aligned almost parallel {centroid–centroid distance = 3.555 (7) Å} are observed (Fig. 2).

Related literature top

For the synthesis of related compounds, see: Cho et al. (2003); Chen et al. (1996). For their biological activity, see: Iwakawa et al. (1994).

Experimental top

To a solution of 4-hydroxybenzothioamide (19.10 mmol) in chloroform (20 ml) at 273 K was added pyridine (3.70 ml, 45.84 mmol) dropwise over a period of 20 min and then p-toluenesulfonyl chloride (22.92 mmol) in small portions. This reaction mixture was stirred at room temperature for 12 h and diluted with dichloromethane and then 10% aqueous HCl. The separated organic layer was washed with 10% aqueous HCl, water and saturated aqueous NaCl. The organic phase was then dried over Na₂SO₄ and concentrated in vacuo. Recrystallization from EtOAc afforded 4-carbamothioylphenyl 4-methylbenzenesulfonate. To the solution of 4-carbamothioylphenyl 4-methylbenzenesulfonate (2 mmol) in THF (10 ml) was added chlorocarbonyl sulfenyl chloride (350 µL, 4 mmol). The mixture was stirred at ambient temperature for 16 h. The solvent was removed in vacuo and the residue was purified by silica-gel column chromatography using EtOAc/hexane as eluent solvent system to get the title compound. Crystals suitable for X-ray analysis were obtained by slow evaporation from a solution in EtOAc at room temperature.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. Molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Crystal structure of the title compound.

4-(5-Oxo-5H-1,2,4-dithiazol-3-yl)phenyl 4-methylbenzenesulfonate top

Crystal data top

C₁₅H₁₁NO₄S₃	D_x = 1.544 Mg m⁻³
M_r = 365.43	Mo Kα radiation, λ = 0.7107 Å
Orthorhombic, Pbcn	Cell parameters from 3356 reflections
a = 30.2449 (9) Å	θ = 2.9–28.8°
b = 7.0841 (3) Å	µ = 0.49 mm⁻¹
c = 14.6755 (5) Å	T = 145 K
V = 3144.36 (18) Å³	Block, colorless
Z = 8	0.25 × 0.20 × 0.20 mm
F(000) = 1504

Data collection top

Agilent Xcalibur Eos diffractometer	2775 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2355 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 16.0874 pixels mm^-1	θ_max = 25.0°, θ_min = 3.0°
ω scans	h = −33→35
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −6→8
T_min = 0.952, T_max = 1.000	l = −10→17
6725 measured reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0338P)² + 1.4416P] where P = (F_o² + 2F_c²)/3
2775 reflections	(Δ/σ)_max = 0.001
209 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₅H₁₁NO₄S₃	V = 3144.36 (18) Å³
M_r = 365.43	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 30.2449 (9) Å	µ = 0.49 mm⁻¹
b = 7.0841 (3) Å	T = 145 K
c = 14.6755 (5) Å	0.25 × 0.20 × 0.20 mm

Data collection top

Agilent Xcalibur Eos diffractometer	2775 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	2355 reflections with I > 2σ(I)
T_min = 0.952, T_max = 1.000	R_int = 0.022
6725 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.04	Δρ_max = 0.41 e Å⁻³
2775 reflections	Δρ_min = −0.29 e Å⁻³
209 parameters

Special details top

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET) (compiled May 16 2011,17:55:39) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	−0.163728 (17)	0.52253 (8)	0.56985 (4)	0.03114 (16)
S2	0.060198 (17)	0.13631 (7)	0.67063 (4)	0.02683 (15)
S3	0.094456 (17)	−0.09859 (7)	0.70721 (4)	0.02913 (15)
O1	−0.20211 (5)	0.5638 (2)	0.51776 (12)	0.0445 (4)
O2	−0.13702 (5)	0.6722 (2)	0.60383 (12)	0.0418 (4)
O3	0.05762 (5)	−0.4287 (2)	0.68332 (12)	0.0405 (4)
O4	−0.13468 (5)	0.3962 (2)	0.50138 (10)	0.0308 (4)
N2	0.01393 (5)	−0.1767 (2)	0.63961 (12)	0.0252 (4)
C1	−0.17634 (6)	0.3654 (3)	0.65777 (15)	0.0255 (5)
C2	−0.15800 (7)	0.3921 (3)	0.74340 (16)	0.0312 (5)
H2	−0.1378	0.4924	0.7540	0.037*
C3	−0.16952 (7)	0.2713 (4)	0.81257 (16)	0.0379 (6)
H3	−0.1574	0.2903	0.8716	0.045*
C4	−0.19842 (7)	0.1220 (4)	0.79851 (17)	0.0388 (6)
C5	−0.21578 (7)	0.0968 (3)	0.71170 (18)	0.0402 (6)
H5	−0.2353	−0.0057	0.7007	0.048*
C6	−0.20530 (7)	0.2173 (3)	0.64109 (16)	0.0324 (5)
H6	−0.2177	0.1993	0.5822	0.039*
C7	−0.21083 (9)	−0.0087 (5)	0.8753 (2)	0.0632 (9)
H7A	−0.2430	−0.0261	0.8761	0.095*
H7B	−0.2012	0.0460	0.9333	0.095*
H7C	−0.1964	−0.1311	0.8664	0.095*
C8	−0.09673 (6)	0.3042 (3)	0.53602 (14)	0.0249 (5)
C9	−0.05942 (6)	0.4055 (3)	0.55942 (15)	0.0287 (5)
H9	−0.0588	0.5390	0.5535	0.034*
C10	−0.02302 (7)	0.3088 (3)	0.59164 (15)	0.0275 (5)
H10	0.0028	0.3762	0.6091	0.033*
C11	−0.02389 (6)	0.1121 (3)	0.59875 (13)	0.0218 (4)
C12	−0.06182 (6)	0.0141 (3)	0.57370 (14)	0.0245 (4)
H12	−0.0625	−0.1197	0.5780	0.029*
C13	−0.09845 (7)	0.1102 (3)	0.54266 (14)	0.0264 (5)
H13	−0.1245	0.0437	0.5261	0.032*
C14	0.01431 (6)	0.0060 (3)	0.63420 (13)	0.0224 (4)
C15	0.05148 (7)	−0.2615 (3)	0.67444 (15)	0.0282 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0248 (3)	0.0286 (3)	0.0401 (3)	0.0061 (2)	0.0028 (2)	0.0039 (3)
S2	0.0256 (3)	0.0214 (3)	0.0335 (3)	0.0013 (2)	−0.0051 (2)	−0.0017 (2)
S3	0.0264 (3)	0.0249 (3)	0.0361 (3)	0.0036 (2)	−0.0070 (2)	−0.0011 (2)
O1	0.0302 (8)	0.0534 (11)	0.0498 (11)	0.0164 (8)	−0.0020 (8)	0.0137 (9)
O2	0.0383 (9)	0.0240 (8)	0.0631 (11)	−0.0013 (7)	0.0100 (9)	−0.0006 (8)
O3	0.0388 (9)	0.0220 (8)	0.0607 (11)	0.0036 (7)	−0.0145 (9)	0.0032 (8)
O4	0.0254 (7)	0.0375 (9)	0.0297 (8)	0.0089 (6)	−0.0002 (7)	0.0033 (7)
N2	0.0254 (9)	0.0224 (9)	0.0279 (10)	0.0009 (7)	−0.0009 (8)	0.0009 (8)
C1	0.0181 (10)	0.0261 (11)	0.0322 (11)	0.0028 (8)	0.0013 (9)	−0.0050 (9)
C2	0.0237 (11)	0.0336 (12)	0.0362 (13)	−0.0027 (9)	−0.0021 (10)	−0.0091 (10)
C3	0.0297 (12)	0.0543 (16)	0.0296 (12)	0.0033 (11)	−0.0023 (11)	−0.0029 (11)
C4	0.0259 (12)	0.0476 (15)	0.0428 (14)	0.0008 (10)	0.0059 (11)	0.0102 (12)
C5	0.0270 (12)	0.0368 (13)	0.0566 (16)	−0.0108 (10)	0.0000 (11)	0.0002 (12)
C6	0.0255 (11)	0.0347 (12)	0.0369 (13)	−0.0022 (10)	−0.0040 (10)	−0.0060 (11)
C7	0.0435 (15)	0.081 (2)	0.065 (2)	−0.0094 (15)	0.0105 (15)	0.0295 (17)
C8	0.0214 (10)	0.0319 (12)	0.0215 (10)	0.0066 (9)	0.0007 (9)	0.0013 (9)
C9	0.0280 (11)	0.0229 (11)	0.0350 (12)	0.0024 (9)	0.0036 (10)	0.0027 (10)
C10	0.0221 (10)	0.0275 (11)	0.0329 (12)	−0.0001 (9)	−0.0001 (9)	−0.0009 (10)
C11	0.0230 (10)	0.0237 (11)	0.0186 (10)	0.0030 (8)	0.0034 (8)	−0.0004 (8)
C12	0.0259 (10)	0.0230 (11)	0.0247 (10)	−0.0002 (8)	0.0027 (9)	−0.0016 (9)
C13	0.0238 (10)	0.0289 (12)	0.0266 (11)	−0.0004 (9)	0.0013 (9)	−0.0017 (9)
C14	0.0223 (10)	0.0263 (11)	0.0185 (10)	0.0002 (8)	0.0030 (8)	−0.0025 (9)
C15	0.0293 (11)	0.0252 (12)	0.0300 (11)	0.0001 (9)	−0.0028 (10)	−0.0007 (9)

Geometric parameters (Å, º) top

S1—O1	1.4204 (16)	C4—C7	1.506 (3)
S1—O2	1.4229 (16)	C5—H5	0.9500
S1—O4	1.6069 (15)	C5—C6	1.380 (3)
S1—C1	1.746 (2)	C6—H6	0.9500
S2—S3	2.0325 (7)	C7—H7A	0.9800
S2—C14	1.7506 (19)	C7—H7B	0.9800
S3—C15	1.803 (2)	C7—H7C	0.9800
O3—C15	1.206 (2)	C8—C9	1.381 (3)
O4—C8	1.414 (2)	C8—C13	1.379 (3)
N2—C14	1.297 (2)	C9—H9	0.9500
N2—C15	1.383 (3)	C9—C10	1.380 (3)
C1—C2	1.387 (3)	C10—H10	0.9500
C1—C6	1.388 (3)	C10—C11	1.398 (3)
C2—H2	0.9500	C11—C12	1.390 (3)
C2—C3	1.373 (3)	C11—C14	1.473 (3)
C3—H3	0.9500	C12—H12	0.9500
C3—C4	1.387 (3)	C12—C13	1.378 (3)
C4—C5	1.390 (3)	C13—H13	0.9500

O1—S1—O2	119.95 (10)	C4—C7—H7B	109.5
O1—S1—O4	103.00 (9)	C4—C7—H7C	109.5
O1—S1—C1	110.51 (10)	H7A—C7—H7B	109.5
O2—S1—O4	108.89 (9)	H7A—C7—H7C	109.5
O2—S1—C1	109.88 (10)	H7B—C7—H7C	109.5
O4—S1—C1	103.08 (9)	C9—C8—O4	120.89 (18)
C14—S2—S3	93.04 (7)	C13—C8—O4	116.98 (18)
C15—S3—S2	94.93 (7)	C13—C8—C9	122.11 (19)
C8—O4—S1	118.39 (13)	C8—C9—H9	120.7
C14—N2—C15	116.67 (17)	C10—C9—C8	118.61 (19)
C2—C1—S1	119.67 (16)	C10—C9—H9	120.7
C2—C1—C6	121.0 (2)	C9—C10—H10	119.8
C6—C1—S1	119.29 (17)	C9—C10—C11	120.38 (19)
C1—C2—H2	120.6	C11—C10—H10	119.8
C3—C2—C1	118.9 (2)	C10—C11—C14	121.35 (18)
C3—C2—H2	120.6	C12—C11—C10	119.56 (18)
C2—C3—H3	119.2	C12—C11—C14	119.07 (17)
C2—C3—C4	121.7 (2)	C11—C12—H12	119.9
C4—C3—H3	119.2	C13—C12—C11	120.30 (19)
C3—C4—C5	118.2 (2)	C13—C12—H12	119.9
C3—C4—C7	121.0 (2)	C8—C13—H13	120.5
C5—C4—C7	120.9 (2)	C12—C13—C8	119.03 (19)
C4—C5—H5	119.3	C12—C13—H13	120.5
C6—C5—C4	121.5 (2)	N2—C14—S2	120.98 (15)
C6—C5—H5	119.3	N2—C14—C11	121.59 (17)
C1—C6—H6	120.7	C11—C14—S2	117.42 (14)
C5—C6—C1	118.7 (2)	O3—C15—S3	119.25 (16)
C5—C6—H6	120.7	O3—C15—N2	126.36 (19)
C4—C7—H7A	109.5	N2—C15—S3	114.38 (15)

Experimental details

Crystal data
Chemical formula	C₁₅H₁₁NO₄S₃
M_r	365.43
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	145
a, b, c (Å)	30.2449 (9), 7.0841 (3), 14.6755 (5)
V (Å³)	3144.36 (18)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Agilent Xcalibur Eos diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.952, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6725, 2775, 2355
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.078, 1.04
No. of reflections	2775
No. of parameters	209
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.29

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Acknowledgements

We thank the Analytical and Testing Center of Sichuan University for the X-ray measurements.

References

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