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

Abstract

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,

• a = 7.0169 (4) Å

• b = 15.5107 (9) Å

• c = 11.0349 (7) Å

• β = 102.391 (3)°

• V = 1173.03 (12) ų

• 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[F ² > 2σ(F ²)] = 0.041

• wR(F ²) = 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

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 .

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

C-bound H atoms were placed in calculated positions (C—H = 0.95–1.00 Å), and included in the final cycles of refinement using a riding model, with U_iso(H) = 1.2U_eq(C) for the aryl and methylene H atoms and 1.5U_eq(C) for the methyl H atoms.

Figures

Fig. 1.

The molecular structure of (I) with displacement ellipsoids drawn at the 40% probability level.

Crystal data

C12H15NS2	F(000) = 504
Mr = 237.37	Dx = 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

Rigaku Saturn diffractometer	2798 independent reflections
Radiation source: rotating anode	2631 reflections with I > 2σ(I)
confocal	Rint = 0.040
Detector resolution: 14.63 pixels mm-1	θmax = 27.9°, θmin = 2.3°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −19→20
Tmin = 0.899, Tmax = 0.967	l = −14→14
14476 measured reflections

Refinement

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(Fo2) + (0.034P)2 + 0.4071P] where P = (Fo2 + 2Fc2)/3
2798 reflections	(Δ/σ)max < 0.001
137 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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

Symmetry codes: (i) x−1, y, z.