3-[1-(4-Chloro­phen­yl)eth­yl]-1,3-thia­zinane-2-thione

Gong, Y.-Y.; Zhang, P.; Wang, M.-H.

doi:10.1107/S1600536811002078

organic compounds

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Volume 67| Part 2| February 2011| Page o514

doi:10.1107/S1600536811002078

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3-[1-(4-Chlorophenyl)ethyl]-1,3-thiazinane-2-thione

Yuan-Yuan Gong,^a Peng Zhang ^a and Ming-Hui Wang ^a ^*

^aCollege of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China
^*Correspondence e-mail: nyhxpyjs@yahoo.com.cn

(Received 6 January 2011; accepted 13 January 2011; online 29 January 2011)

In the title compound, C₁₂H₁₄ClNS₂, the thiazole ring adopts an envelope conformation; the basal plane is nearly perpendicular to the benzene ring at a dihedral angle of 85.72 (5)°. Weak intermolecular C—H⋯S hydrogen bonding is present in the crystal structure.

Related literature

For the biological activity of thiazole compounds, see: Amir et al. (2006 ). For a related structure, see: Cunico et al. (2007 ).

Experimental

Crystal data

C₁₂H₁₄ClNS₂
M_r = 271.81
Orthorhombic, P b c a
a = 11.260 (2) Å
b = 11.888 (2) Å
c = 18.978 (4) Å
V = 2540.5 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.60 mm⁻¹
T = 113 K
0.18 × 0.14 × 0.12 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.900, T_max = 0.931
16988 measured reflections
2932 independent reflections
2605 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.089
S = 1.11
2925 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯S2ⁱ	0.97	2.85	3.773 (2)	158
C10—H10B⋯S2ⁱⁱ	0.97	2.77	3.701 (2)	160
Symmetry codes: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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/S1600536811002078/xu5140sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811002078/xu5140Isup2.hkl

checkCIF report

Comment top

Recently, compounds containing a 1,3-thiazinane group have attracted much interest because the 1,3-thiazinane ring system are well known as its efficient insecticidal activity for a wide variety of crops (Amir et al., 2006). The title compound (I) was synthesized as a new compound with better biological activity. We report here the crystal structure of (I).

In (I) all bond lengths and angles are normal and in a good agreement with those reported previously (Cunico et al., 2007). The thiazole ring is in and envelope conformation with the –CH₂– group bonded to the S1 atom forming the flap. The 1,3-thiazinane-2-thione ring forms two dihedral angles are 85.99 (2)° [S1/S2/N1/C7/C9/C11/C12] and 77.68 (2)° [N1/C9/C10/C11/C12] with the benzene ring respectively. The crystal structure is stabilized by weak intermolecular C–H···S hydrogen bonds.

Related literature top

For the biological activity of thiazole compounds, see: Amir et al. (2006). For a related structure, see: Cunico et al. (2007).

Experimental top

1,3-Thiazinane-2-thione 1.33 g (10.0 mmol) and deacid reagent potassium carbonate 1.38 g (5.0 mmol) were added in a flask equipped with stirrer, the solvent acetonitrile (20 ml) was added and the mixture was stirred for 0.5 h. Then 1-chloro-4-(1-chloroethyl)benzene 1.74 g (10.0 mmol) was added dropwising within 2 h at 333 K. The mixture was stirred for 8 h at 433 K. Upon cooling at room temperature. then the solid was filterred, the filter-cake was washed twice by acetonitrile. Crystallized from methanol to afford the title compound 2.0 g (74% yield) Single crystals suitable for X-ray measurement were obtained by recrystallization from the mixture of acetone and methanol at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 displacement ellipsoids drawn at the 40% probability level.

3-[1-(4-Chlorophenyl)ethyl]-1,3-thiazinane-2-thione top

Crystal data top

C₁₂H₁₄ClNS₂	F(000) = 1136
M_r = 271.81	D_x = 1.421 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5973 reflections
a = 11.260 (2) Å	θ = 2.2–27.5°
b = 11.888 (2) Å	µ = 0.60 mm⁻¹
c = 18.978 (4) Å	T = 113 K
V = 2540.5 (9) Å³	Block, colorless
Z = 8	0.18 × 0.14 × 0.12 mm

Data collection top

Rigaku Saturn diffractometer	2932 independent reflections
Radiation source: rotating anode	2605 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.050
ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −14→14
T_min = 0.900, T_max = 0.931	k = −7→15
16988 measured reflections	l = −24→24

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0383P)² + 0.9612P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.002
2925 reflections	Δρ_max = 0.29 e Å⁻³
147 parameters	Δρ_min = −0.26 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0031 (5)

Crystal data top

C₁₂H₁₄ClNS₂	V = 2540.5 (9) Å³
M_r = 271.81	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.260 (2) Å	µ = 0.60 mm⁻¹
b = 11.888 (2) Å	T = 113 K
c = 18.978 (4) Å	0.18 × 0.14 × 0.12 mm

Data collection top

Rigaku Saturn diffractometer	2932 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2605 reflections with I > 2σ(I)
T_min = 0.900, T_max = 0.931	R_int = 0.050
16988 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.11	Δρ_max = 0.29 e Å⁻³
2925 reflections	Δρ_min = −0.26 e Å⁻³
147 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
Cl1	−0.02163 (5)	0.84121 (4)	0.54940 (3)	0.03747 (15)
S1	0.12139 (4)	0.46585 (4)	0.16831 (2)	0.02721 (14)
S2	−0.00573 (4)	0.34132 (4)	0.27142 (2)	0.02514 (13)
N1	0.17516 (12)	0.47749 (11)	0.30690 (7)	0.0190 (3)
C1	0.03561 (15)	0.61986 (15)	0.39541 (9)	0.0223 (4)
H1	0.0095	0.6085	0.3495	0.027*
C2	−0.00917 (15)	0.70925 (15)	0.43370 (10)	0.0244 (4)
H2	−0.0652	0.7573	0.4140	0.029*
C3	0.03060 (16)	0.72615 (14)	0.50171 (10)	0.0247 (4)
C4	0.11393 (16)	0.65588 (15)	0.53172 (9)	0.0263 (4)
H4	0.1405	0.6684	0.5774	0.032*
C5	0.15754 (16)	0.56606 (15)	0.49268 (9)	0.0239 (4)
H5	0.2135	0.5183	0.5127	0.029*
C6	0.11905 (14)	0.54630 (13)	0.42412 (9)	0.0191 (3)
C7	0.15969 (15)	0.44518 (14)	0.38191 (9)	0.0211 (4)
H7	0.0951	0.3900	0.3836	0.025*
C8	0.27095 (17)	0.38623 (17)	0.40901 (10)	0.0317 (4)
H8A	0.2939	0.3284	0.3765	0.047*
H8B	0.2548	0.3533	0.4542	0.047*
H8C	0.3342	0.4399	0.4135	0.047*
C9	0.27378 (15)	0.55691 (15)	0.29311 (9)	0.0229 (4)
H9A	0.3458	0.5144	0.2843	0.027*
H9B	0.2868	0.6025	0.3348	0.027*
C10	0.25045 (16)	0.63354 (15)	0.23103 (9)	0.0258 (4)
H10A	0.3144	0.6878	0.2270	0.031*
H10B	0.1771	0.6745	0.2387	0.031*
C11	0.24125 (17)	0.56687 (17)	0.16328 (10)	0.0305 (4)
H11A	0.3155	0.5278	0.1547	0.037*
H11B	0.2273	0.6178	0.1242	0.037*
C12	0.10630 (14)	0.43289 (14)	0.25731 (9)	0.0194 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0465 (3)	0.0281 (3)	0.0379 (3)	0.0064 (2)	0.0101 (2)	−0.0076 (2)
S1	0.0275 (3)	0.0321 (3)	0.0220 (2)	−0.00856 (19)	−0.00050 (18)	−0.00137 (18)
S2	0.0221 (2)	0.0233 (2)	0.0301 (2)	−0.00669 (17)	−0.00089 (18)	−0.00064 (17)
N1	0.0159 (7)	0.0190 (7)	0.0222 (7)	−0.0002 (5)	−0.0002 (6)	−0.0020 (6)
C1	0.0184 (8)	0.0250 (8)	0.0236 (9)	−0.0008 (7)	−0.0032 (7)	−0.0004 (7)
C2	0.0185 (8)	0.0219 (8)	0.0327 (10)	0.0015 (7)	0.0007 (7)	0.0034 (7)
C3	0.0264 (9)	0.0197 (8)	0.0282 (9)	−0.0021 (7)	0.0084 (7)	−0.0006 (7)
C4	0.0304 (10)	0.0293 (9)	0.0192 (8)	−0.0021 (8)	0.0022 (7)	0.0013 (7)
C5	0.0253 (9)	0.0246 (8)	0.0220 (8)	0.0020 (7)	−0.0003 (7)	0.0042 (7)
C6	0.0161 (8)	0.0198 (8)	0.0215 (8)	−0.0023 (6)	0.0012 (7)	0.0028 (7)
C7	0.0213 (9)	0.0204 (8)	0.0215 (8)	−0.0001 (7)	−0.0020 (7)	0.0007 (7)
C8	0.0342 (11)	0.0283 (9)	0.0325 (10)	0.0106 (8)	−0.0070 (8)	−0.0031 (8)
C9	0.0159 (8)	0.0247 (8)	0.0280 (9)	−0.0043 (7)	0.0015 (7)	−0.0042 (7)
C10	0.0214 (9)	0.0206 (8)	0.0353 (10)	−0.0045 (7)	0.0038 (8)	−0.0005 (8)
C11	0.0269 (10)	0.0359 (10)	0.0287 (9)	−0.0090 (8)	0.0034 (8)	0.0026 (8)
C12	0.0172 (8)	0.0158 (7)	0.0253 (8)	0.0024 (6)	−0.0003 (7)	−0.0020 (7)

Geometric parameters (Å, º) top

Cl1—C3	1.7425 (18)	C5—H5	0.9300
S1—C12	1.7422 (18)	C6—C7	1.515 (2)
S1—C11	1.8092 (19)	C7—C8	1.525 (2)
S2—C12	1.6875 (17)	C7—H7	0.9800
N1—C12	1.330 (2)	C8—H8A	0.9600
N1—C9	1.481 (2)	C8—H8B	0.9600
N1—C7	1.485 (2)	C8—H8C	0.9600
C1—C2	1.383 (2)	C9—C10	1.512 (3)
C1—C6	1.394 (2)	C9—H9A	0.9700
C1—H1	0.9300	C9—H9B	0.9700
C2—C3	1.381 (3)	C10—C11	1.514 (3)
C2—H2	0.9300	C10—H10A	0.9700
C3—C4	1.379 (3)	C10—H10B	0.9700
C4—C5	1.389 (2)	C11—H11A	0.9700
C4—H4	0.9300	C11—H11B	0.9700
C5—C6	1.391 (2)

C12—S1—C11	105.85 (8)	C7—C8—H8A	109.5
C12—N1—C9	124.50 (14)	C7—C8—H8B	109.5
C12—N1—C7	120.47 (14)	H8A—C8—H8B	109.5
C9—N1—C7	114.98 (13)	C7—C8—H8C	109.5
C2—C1—C6	121.49 (16)	H8A—C8—H8C	109.5
C2—C1—H1	119.3	H8B—C8—H8C	109.5
C6—C1—H1	119.3	N1—C9—C10	113.05 (14)
C3—C2—C1	119.00 (16)	N1—C9—H9A	109.0
C3—C2—H2	120.5	C10—C9—H9A	109.0
C1—C2—H2	120.5	N1—C9—H9B	109.0
C4—C3—C2	121.23 (16)	C10—C9—H9B	109.0
C4—C3—Cl1	119.37 (15)	H9A—C9—H9B	107.8
C2—C3—Cl1	119.36 (14)	C9—C10—C11	110.98 (15)
C3—C4—C5	119.06 (17)	C9—C10—H10A	109.4
C3—C4—H4	120.5	C11—C10—H10A	109.4
C5—C4—H4	120.5	C9—C10—H10B	109.4
C4—C5—C6	121.22 (16)	C11—C10—H10B	109.4
C4—C5—H5	119.4	H10A—C10—H10B	108.0
C6—C5—H5	119.4	C10—C11—S1	110.72 (12)
C5—C6—C1	117.99 (16)	C10—C11—H11A	109.5
C5—C6—C7	122.29 (15)	S1—C11—H11A	109.5
C1—C6—C7	119.64 (15)	C10—C11—H11B	109.5
N1—C7—C6	109.69 (13)	S1—C11—H11B	109.5
N1—C7—C8	110.24 (14)	H11A—C11—H11B	108.1
C6—C7—C8	115.75 (14)	N1—C12—S2	125.51 (13)
N1—C7—H7	106.9	N1—C12—S1	122.66 (13)
C6—C7—H7	106.9	S2—C12—S1	111.83 (9)
C8—C7—H7	106.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···S2ⁱ	0.97	2.85	3.773 (2)	158
C10—H10B···S2ⁱⁱ	0.97	2.77	3.701 (2)	160

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄ClNS₂
M_r	271.81
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	113
a, b, c (Å)	11.260 (2), 11.888 (2), 18.978 (4)
V (Å³)	2540.5 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.60
Crystal size (mm)	0.18 × 0.14 × 0.12

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.900, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	16988, 2932, 2605
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.089, 1.11
No. of reflections	2925
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.26

Computer programs: CrystalClear (Rigaku, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···S2ⁱ	0.97	2.85	3.773 (2)	158
C10—H10B···S2ⁱⁱ	0.97	2.77	3.701 (2)	160

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

References

Amir, N., Motonishi, M., Fujita, M., Miyashita, Y., Fujisawa, K. & Okamoto, K. (2006). Eur. J. Inorg. Chem. pp. 1041–1049. Web of Science CSD CrossRef Google Scholar
Cunico, W., Gomes, C. R. B., Wardell, S. M. S. V., Low, J. N. & Glidewell, C. (2007). Acta Cryst. C63, o411–o414. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o514

doi:10.1107/S1600536811002078

Open

access