3-(1-Phenyl­ethyl)-1,3-thia­zinane-2-thione

Yan, F.; Liang, C.

doi:10.1107/S1600536809046248

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3066

doi:10.1107/S1600536809046248

Open

access

3-(1-Phenylethyl)-1,3-thiazinane-2-thione

Fu-feng Yan ^a ^* and Chong-jia Liang ^b

^aProvincial Key Laboratory of Surface & Interface Science, Zhengzhou University of Light Industry, Zhengzhou 450002, People's Republic of China, and ^bHenan Sports School, Zhengzhou 450044, People's Republic of China
^*Correspondence e-mail: yanfufeng@yahoo.cn

(Received 28 October 2009; accepted 3 November 2009; online 11 November 2009)

In the title molecule, C₁₂H₁₅NS₂, the 1,3-thiazinane ring has a half-boat conformation; the C atom at position 5 deviates by 0.715 (2) Å from the mean plane (P) of the remaining five atoms. Plane P and the phenyl ring form a dihedral angle of 83.62 (3)°. In the crystal structure, weak intermolecular C—H⋯S hydrogen bonds link molecules related by translation along the axis a into chains.

Related literature

For the crystal structures of related thiazinane derivatives, see: Kálmán et al. (1977 ); Peng & Wu (2009 ); Amir et al. (2006 ). For the biological activity of thiazinane-containing compounds, see: Soloway et al. (1978 ); Tomizawa et al. (1995 ).

Experimental

Crystal data

C₁₂H₁₅NS₂
M_r = 237.37
Monoclinic, P 2₁ /n
a = 7.0169 (4) Å
b = 15.5107 (9) Å
c = 11.0349 (7) Å
β = 102.391 (3)°
V = 1173.03 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 113 K
0.26 × 0.10 × 0.08 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.899, T_max = 0.967
14476 measured reflections
2798 independent reflections
2631 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.087
S = 1.13
2798 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6C⋯S1ⁱ	0.98	2.76	3.7279 (17)	168
Symmetry code: (i) x-1, y, z.

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/S1600536809046248/cv2647sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809046248/cv2647Isup2.hkl

checkCIF report

Comment top

Many compounds containing thiazinane groups possess a broad spectrum of biological activities (Soloway et al., 1978; Tomizawa et al., 1995). Herein we report the crystal structure of the title compound, (I).

In (I) (Fig. 1), all bond lengths and angles are in a good agreement with those reported previously (Kálmán et al., 1977; Peng & Wu, 2009; Amir et al., 2006). The thiazinane ring shows a conformation near to a half boat with the carbon atom at position 5 (C3) deviating 0.715 (2) Å above the plane p1 formed by S2, N1, C1, C2 and C4 [maximum least squares plane deviation for S2 0.038 (3) Å]. The dihedral angle between the benzene ring C7-C12 and plane p1 is 83.62 (3) °. In the crystal structure, weak intermolecular C—H···S hydrogen bonds link molecules related by translation along axis a into chains.

Related literature top

For the crystal structures of related thiazinane derivatives, see: Kálmán et al. (1977); Peng & Wu (2009); Amir et al. (2006). For the biological activity of thiazinane-containing compounds, see: Soloway et al. (1978); Tomizawa et al. (1995).

Experimental top

A solution of 1,3-thiazinane-2-thione (1.33 g, 10 mmol) and sodium hydride (0.3 g) dissolved in anhydrous acetonitrile (20 ml), and dropwise added over a period of 10 min to a solution of 1-(1-chloroethyl)benzene (1.41g, 10 mmol) in acetonitrile (10 ml) at 273 K. The mixture was stirred at 353 K for 2 h. The solvent was removed and the residue was purified by flash chromatography (3:1 Cyclohexane:Dichloromethane) to give title compound as a white solid (1.90 g, 80%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol 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-Phenylethyl)-1,3-thiazinane-2-thione top

Crystal data top

C₁₂H₁₅NS₂	F(000) = 504
M_r = 237.37	D_x = 1.344 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2yn	Cell parameters from 3792 reflections
a = 7.0169 (4) Å	θ = 2.3–27.9°
b = 15.5107 (9) Å	µ = 0.42 mm⁻¹
c = 11.0349 (7) Å	T = 113 K
β = 102.391 (3)°	Prism, colourless
V = 1173.03 (12) Å³	0.26 × 0.10 × 0.08 mm
Z = 4

Data collection top

Rigaku Saturn diffractometer	2798 independent reflections
Radiation source: rotating anode	2631 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.040
Detector resolution: 14.63 pixels mm^-1	θ_max = 27.9°, θ_min = 2.3°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −19→20
T_min = 0.899, T_max = 0.967	l = −14→14
14476 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.034P)² + 0.4071P] where P = (F_o² + 2F_c²)/3
2798 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₂H₁₅NS₂	V = 1173.03 (12) Å³
M_r = 237.37	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.0169 (4) Å	µ = 0.42 mm⁻¹
b = 15.5107 (9) Å	T = 113 K
c = 11.0349 (7) Å	0.26 × 0.10 × 0.08 mm
β = 102.391 (3)°

Data collection top

Rigaku Saturn diffractometer	2798 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2631 reflections with I > 2σ(I)
T_min = 0.899, T_max = 0.967	R_int = 0.040
14476 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.13	Δρ_max = 0.27 e Å⁻³
2798 reflections	Δρ_min = −0.32 e Å⁻³
137 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
S1	1.23060 (6)	0.17662 (3)	0.70183 (4)	0.03009 (13)
S2	1.02102 (6)	0.13716 (3)	0.45696 (4)	0.02633 (12)
N1	0.86777 (18)	0.11187 (8)	0.65929 (12)	0.0193 (3)
C1	1.0203 (2)	0.13813 (10)	0.61536 (15)	0.0208 (3)
C2	0.6824 (2)	0.08125 (10)	0.58027 (14)	0.0215 (3)
H2A	0.5755	0.0905	0.6247	0.026*
H2B	0.6923	0.0185	0.5663	0.026*
C3	0.6315 (2)	0.12648 (10)	0.45586 (15)	0.0225 (3)
H3A	0.4993	0.1088	0.4115	0.027*
H3B	0.6302	0.1896	0.4690	0.027*
C4	0.7771 (2)	0.10468 (11)	0.37795 (15)	0.0262 (4)
H4A	0.7410	0.1346	0.2970	0.031*
H4B	0.7749	0.0418	0.3621	0.031*
C5	0.8766 (2)	0.11054 (10)	0.79582 (14)	0.0207 (3)
H5	1.0167	0.1176	0.8383	0.025*
C6	0.7662 (2)	0.18756 (10)	0.83194 (15)	0.0245 (3)
H6A	0.8277	0.2410	0.8124	0.037*
H6B	0.7692	0.1854	0.9211	0.037*
H6C	0.6305	0.1858	0.7855	0.037*
C7	0.8115 (2)	0.02299 (10)	0.83270 (14)	0.0203 (3)
C8	0.9420 (3)	−0.04584 (11)	0.84269 (15)	0.0250 (4)
H8	1.0682	−0.0366	0.8268	0.030*
C9	0.8901 (3)	−0.12754 (11)	0.87548 (16)	0.0316 (4)
H9	0.9796	−0.1740	0.8804	0.038*
C10	0.7074 (3)	−0.14124 (11)	0.90105 (16)	0.0316 (4)
H10	0.6718	−0.1970	0.9243	0.038*
C11	0.5777 (3)	−0.07356 (11)	0.89258 (15)	0.0283 (4)
H11	0.4528	−0.0828	0.9105	0.034*
C12	0.6284 (2)	0.00820 (10)	0.85792 (14)	0.0235 (3)
H12	0.5373	0.0542	0.8515	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0166 (2)	0.0355 (3)	0.0367 (3)	−0.00502 (17)	0.00244 (18)	−0.00113 (19)
S2	0.0240 (2)	0.0303 (2)	0.0266 (2)	−0.00098 (17)	0.00950 (17)	0.00309 (17)
N1	0.0157 (6)	0.0211 (6)	0.0203 (6)	−0.0016 (5)	0.0020 (5)	−0.0005 (5)
C1	0.0177 (7)	0.0165 (7)	0.0282 (8)	0.0027 (6)	0.0048 (6)	0.0007 (6)
C2	0.0181 (7)	0.0238 (8)	0.0217 (8)	−0.0045 (6)	0.0022 (6)	−0.0013 (6)
C3	0.0214 (8)	0.0218 (8)	0.0225 (8)	−0.0018 (6)	0.0009 (6)	0.0000 (6)
C4	0.0290 (9)	0.0280 (9)	0.0211 (8)	−0.0021 (7)	0.0043 (7)	0.0007 (7)
C5	0.0178 (7)	0.0244 (8)	0.0188 (7)	0.0005 (6)	0.0015 (6)	−0.0017 (6)
C6	0.0259 (8)	0.0218 (8)	0.0245 (8)	0.0006 (7)	0.0025 (7)	−0.0032 (6)
C7	0.0224 (8)	0.0226 (8)	0.0149 (7)	0.0008 (6)	0.0016 (6)	−0.0019 (6)
C8	0.0257 (8)	0.0275 (8)	0.0204 (8)	0.0067 (7)	0.0019 (6)	−0.0023 (6)
C9	0.0421 (11)	0.0241 (8)	0.0249 (8)	0.0105 (8)	−0.0008 (8)	−0.0027 (7)
C10	0.0484 (11)	0.0207 (8)	0.0227 (8)	−0.0016 (8)	0.0012 (8)	0.0016 (7)
C11	0.0328 (9)	0.0301 (9)	0.0225 (8)	−0.0051 (7)	0.0071 (7)	0.0019 (7)
C12	0.0251 (8)	0.0241 (8)	0.0210 (8)	0.0033 (7)	0.0043 (6)	0.0002 (6)

Geometric parameters (Å, º) top

S1—C1	1.6851 (16)	C5—H5	1.0000
S2—C1	1.7491 (17)	C6—H6A	0.9800
S2—C4	1.8172 (17)	C6—H6B	0.9800
N1—C1	1.330 (2)	C6—H6C	0.9800
N1—C2	1.4803 (19)	C7—C12	1.390 (2)
N1—C5	1.495 (2)	C7—C8	1.395 (2)
C2—C3	1.515 (2)	C8—C9	1.388 (2)
C2—H2A	0.9900	C8—H8	0.9500
C2—H2B	0.9900	C9—C10	1.387 (3)
C3—C4	1.508 (2)	C9—H9	0.9500
C3—H3A	0.9900	C10—C11	1.379 (3)
C3—H3B	0.9900	C10—H10	0.9500
C4—H4A	0.9900	C11—C12	1.393 (2)
C4—H4B	0.9900	C11—H11	0.9500
C5—C7	1.516 (2)	C12—H12	0.9500
C5—C6	1.523 (2)

C1—S2—C4	106.11 (8)	N1—C5—H5	107.2
C1—N1—C2	123.90 (13)	C7—C5—H5	107.2
C1—N1—C5	120.59 (13)	C6—C5—H5	107.2
C2—N1—C5	115.50 (12)	C5—C6—H6A	109.5
N1—C1—S1	125.27 (13)	C5—C6—H6B	109.5
N1—C1—S2	122.45 (12)	H6A—C6—H6B	109.5
S1—C1—S2	112.27 (9)	C5—C6—H6C	109.5
N1—C2—C3	113.06 (13)	H6A—C6—H6C	109.5
N1—C2—H2A	109.0	H6B—C6—H6C	109.5
C3—C2—H2A	109.0	C12—C7—C8	118.47 (15)
N1—C2—H2B	109.0	C12—C7—C5	123.11 (14)
C3—C2—H2B	109.0	C8—C7—C5	118.42 (14)
H2A—C2—H2B	107.8	C9—C8—C7	120.99 (16)
C4—C3—C2	110.86 (13)	C9—C8—H8	119.5
C4—C3—H3A	109.5	C7—C8—H8	119.5
C2—C3—H3A	109.5	C10—C9—C8	119.90 (16)
C4—C3—H3B	109.5	C10—C9—H9	120.0
C2—C3—H3B	109.5	C8—C9—H9	120.0
H3A—C3—H3B	108.1	C11—C10—C9	119.66 (16)
C3—C4—S2	110.36 (11)	C11—C10—H10	120.2
C3—C4—H4A	109.6	C9—C10—H10	120.2
S2—C4—H4A	109.6	C10—C11—C12	120.52 (17)
C3—C4—H4B	109.6	C10—C11—H11	119.7
S2—C4—H4B	109.6	C12—C11—H11	119.7
H4A—C4—H4B	108.1	C7—C12—C11	120.44 (15)
N1—C5—C7	109.47 (12)	C7—C12—H12	119.8
N1—C5—C6	109.85 (13)	C11—C12—H12	119.8
C7—C5—C6	115.64 (13)

C2—N1—C1—S1	177.75 (11)	C2—N1—C5—C6	−78.27 (16)
C5—N1—C1—S1	−3.2 (2)	N1—C5—C7—C12	−103.30 (16)
C2—N1—C1—S2	−1.5 (2)	C6—C5—C7—C12	21.4 (2)
C5—N1—C1—S2	177.55 (11)	N1—C5—C7—C8	77.19 (17)
C4—S2—C1—N1	4.98 (15)	C6—C5—C7—C8	−158.12 (14)
C4—S2—C1—S1	−174.33 (8)	C12—C7—C8—C9	0.8 (2)
C1—N1—C2—C3	−33.2 (2)	C5—C7—C8—C9	−179.67 (15)
C5—N1—C2—C3	147.72 (13)	C7—C8—C9—C10	−1.2 (3)
N1—C2—C3—C4	66.05 (17)	C8—C9—C10—C11	0.6 (3)
C2—C3—C4—S2	−59.48 (16)	C9—C10—C11—C12	0.4 (3)
C1—S2—C4—C3	25.10 (14)	C8—C7—C12—C11	0.2 (2)
C1—N1—C5—C7	−129.39 (14)	C5—C7—C12—C11	−179.36 (15)
C2—N1—C5—C7	49.72 (17)	C10—C11—C12—C7	−0.7 (2)
C1—N1—C5—C6	102.62 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6C···S1ⁱ	0.98	2.76	3.7279 (17)	168

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅NS₂
M_r	237.37
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	7.0169 (4), 15.5107 (9), 11.0349 (7)
β (°)	102.391 (3)
V (Å³)	1173.03 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.42
Crystal size (mm)	0.26 × 0.10 × 0.08

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.899, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	14476, 2798, 2631
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.087, 1.13
No. of reflections	2798
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.32

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
C6—H6C···S1ⁱ	0.98	2.76	3.7279 (17)	168.3

Symmetry code: (i) x−1, y, z.

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
Kálmán, A., Argay, G., Riba'r, B. & Toldy, L. (1977). Tetrahedron Lett. 48, 4241–4244. Google Scholar
Peng, Y. & Wu, L. (2009). Acta Cryst. E65, o784. 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
Soloway, S. B., Henry, A. C., Kollmeyer, W. D., Padgett, W. M., Powell, J. E., Roman, S. A., Tiemann, C. H., Corey, R. A. & Horne, C. A. (1978). Nitromethylene Heterocycles as Insecticides, in Pesticide and Venom Neurotoxicology, edited by D. L. Shankland, R. M. Hollingworth & T. Smyth Jr, pp. 153–158. New York: Plenum Press. Google Scholar
Tomizawa, M., Otsuka, H., Miyamoto, T. & Yamamoto, I. (1995). J. Pesticide Sci. 20, 49–56. CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3066

doi:10.1107/S1600536809046248

Open

access