(Z)-2-[(2,4-Dimethyl­phen­yl)imino]-1,3-thia­zinan-4-one

Zhao, H.-R.; Meng, X.-W.

doi:10.1107/S1600536810051147

organic compounds

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Volume 67| Part 1| January 2011| Page o110

https://doi.org/10.1107/S1600536810051147

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(Z)-2-[(2,4-Dimethylphenyl)imino]-1,3-thiazinan-4-one

Hua-Rong Zhao ^a ^* and Xiang-Wu Meng ^a

^aDepartment of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China
^*Correspondence e-mail: zhr0103@zju.edu.cn

(Received 22 November 2010; accepted 6 December 2010; online 11 December 2010)

In the title compound, C₁₂H₁₄N₂OS, the 1,3-thiazinane ring displays a screw-boat conformation. In the crystal, pairs of centrosymmetrically related molecules are linked by pairs of N—H⋯O hydrogen bonds into dimers. C—H⋯π interactions occur between adjacent dimers.

Related literature

For pharmaceutical applications of 4-thiazinones, see: Mogilaiah et al. (1999 ); Turkevich et al., 1977). For the synthesis, see: Mansuroğlu et al. (2009 ); Schroth et al. (1977 ).

Experimental

Crystal data

C₁₂H₁₄N₂OS
M_r = 234.31
Triclinic, $[P \overline 1]$
a = 7.2325 (4) Å
b = 9.2000 (7) Å
c = 10.0513 (7) Å
α = 114.184 (7)°
β = 94.647 (5)°
γ = 97.910 (5)°
V = 597.27 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 K
0.48 × 0.28 × 0.23 mm

Data collection

Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.919, T_max = 0.944
4061 measured reflections
2188 independent reflections
1569 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.115
S = 1.06
2188 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C2–C7 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.86	2.08	2.900 (3)	161
C1—H1C⋯Cg2ⁱⁱ	0.96	2.72	3.591 (3)	152
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) -x+2, -y, -z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ); 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: https://doi.org/10.1107/S1600536810051147/xu5100sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810051147/xu5100Isup2.hkl

checkCIF report

Comment top

4-Thiazinones have remarkable biological activities such as antithyroid (Turkevich et al., 1977) and antimicrobial activity (Mogilaiah et al., 1999). We report here the structure of a new derivative of 4-thiazinones (Fig. 1).

In the title compound, the thiazine ring is non-planar. Theoretically, there may be two tautomers according to the title compound, the C=N double bond can exist between C9 and N1 or between C9 and N2, however, from the experimental data, the bond length 1.264 (3) Å indicates that the double bond between C9 and N1. Intermolecular N—H···O hydrogen bonds (Table 1), link two molecules to form a dimer, and the dimer forms two-dimensional supra-molecular layers.

Related literature top

For pharmaceutical applications of 4-thiazinones, see: Mogilaiah et al. (1999); Turkevich et al., 1977). For the synthesis, see: Mansuroğlu et al. (2009); Schroth et al. (1977).

Experimental top

The title compound was prepared according to the procedure reported by Mansuroğlu et al. (2009) and Schroth et al. (1977). A solution of 3-chloropropionyl chloride (0.125 g,1 mmol) in acetone (5 ml) was added dropwise to a suspension of potassium thiocyanate (0.145 g,1.5 mmol).The reaction mixture was heated under reflux for 30 min and then cooled to room temperature. A solution of 2,4-dimethylaniline (0.121 g,1 mmol) in acetone (3 ml) was added to the mixture during a period of 15 min at room temperature and the mixture was stirred for 2 h. Hydrochloric acid (0.1 N, 30 ml) was added, and the solution was filtered. The solid product N-(3-chloropropionyl)-N'-(2,4-dimethylphenyl)thiourea was washed with water and purified by recrystallization from ethanol:dichloromethane(1:1) mixture. Then the thiourea (0.216 g, 0.8 mmol) was put in a 50 ml flask. Toluene (30 ml) and acetone (2 ml) were added to the flask. The solution of thiourea was refluxed for 4 h. On completion, cool the reaction mixture, vaporize the solvent under reduced pressure, we can get the crude product, then, the crude product is chromatographed on silica gel (eluent, petroleum ether:ethyl acetate=1:1). Recrystallization of the product from ethanol gave white crystalline solids.

Structure description top

For pharmaceutical applications of 4-thiazinones, see: Mogilaiah et al. (1999); Turkevich et al., 1977). For the synthesis, see: Mansuroğlu et al. (2009); Schroth et al. (1977).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2008); cell refinement: CrysAlis PRO (Oxford Diffraction, 2008); data reduction: CrysAlis PRO (Oxford Diffraction, 2008); 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. The molecular structure of the title compound with 40% probability displacement ellipsoids.

(Z)-2-[(2,4-Dimethylphenyl)imino]-1,3-thiazinan-4-one top

Crystal data top

C₁₂H₁₄N₂OS	Z = 2
M_r = 234.31	F(000) = 248
Triclinic, P1	D_x = 1.303 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2325 (4) Å	Cell parameters from 1436 reflections
b = 9.2000 (7) Å	θ = 2.8–29.2°
c = 10.0513 (7) Å	µ = 0.25 mm⁻¹
α = 114.184 (7)°	T = 293 K
β = 94.647 (5)°	Block, colorless
γ = 97.910 (5)°	0.48 × 0.28 × 0.23 mm
V = 597.27 (7) Å³

Data collection top

Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer	2188 independent reflections
Radiation source: fine-focus sealed tube	1569 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 10.3592 pixels mm^-1	θ_max = 25.4°, θ_min = 2.9°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2008)	k = −10→11
T_min = 0.919, T_max = 0.944	l = −12→9
4061 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0414P)² + 0.175P] where P = (F_o² + 2F_c²)/3
2188 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₂H₁₄N₂OS	γ = 97.910 (5)°
M_r = 234.31	V = 597.27 (7) Å³
Triclinic, P1	Z = 2
a = 7.2325 (4) Å	Mo Kα radiation
b = 9.2000 (7) Å	µ = 0.25 mm⁻¹
c = 10.0513 (7) Å	T = 293 K
α = 114.184 (7)°	0.48 × 0.28 × 0.23 mm
β = 94.647 (5)°

Data collection top

Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer	2188 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2008)	1569 reflections with I > 2σ(I)
T_min = 0.919, T_max = 0.944	R_int = 0.026
4061 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.06	Δρ_max = 0.21 e Å⁻³
2188 reflections	Δρ_min = −0.28 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
S1	0.55185 (9)	0.52363 (7)	0.33010 (8)	0.0523 (3)
O1	0.8076 (2)	1.03840 (19)	0.5892 (2)	0.0549 (5)
N1	0.9131 (3)	0.5481 (2)	0.2917 (2)	0.0440 (5)
N2	0.8280 (3)	0.7918 (2)	0.4195 (2)	0.0421 (5)
H2	0.9236	0.8376	0.3961	0.051*
C1	0.7441 (4)	−0.1475 (3)	0.0075 (4)	0.0823 (11)
H1A	0.6145	−0.1836	−0.0386	0.123*
H1B	0.7650	−0.1892	0.0797	0.123*
H1C	0.8247	−0.1863	−0.0658	0.123*
C2	0.7884 (3)	0.0354 (3)	0.0820 (3)	0.0518 (7)
C3	0.8622 (4)	0.1187 (3)	0.2294 (3)	0.0580 (8)
H3	0.8850	0.0615	0.2848	0.070*
C4	0.9027 (4)	0.2862 (3)	0.2960 (3)	0.0501 (7)
H4	0.9552	0.3403	0.3952	0.060*
C5	0.8663 (3)	0.3743 (3)	0.2171 (3)	0.0399 (6)
C6	0.7938 (3)	0.2946 (3)	0.0679 (3)	0.0445 (6)
C7	0.7569 (3)	0.1258 (3)	0.0048 (3)	0.0540 (8)
H7	0.7082	0.0710	−0.0951	0.065*
C8	0.7535 (4)	0.3858 (4)	−0.0223 (3)	0.0680 (9)
H8B	0.7962	0.3363	−0.1158	0.102*
H8C	0.8184	0.4964	0.0293	0.102*
H8A	0.6201	0.3829	−0.0379	0.102*
C9	0.7833 (3)	0.6224 (3)	0.3455 (3)	0.0360 (6)
C10	0.4370 (3)	0.6924 (3)	0.4178 (3)	0.0544 (7)
H10B	0.4074	0.7384	0.3491	0.065*
H10A	0.3191	0.6545	0.4433	0.065*
C11	0.5592 (3)	0.8223 (3)	0.5554 (3)	0.0477 (7)
H11B	0.4893	0.9078	0.6024	0.057*
H11A	0.5883	0.7760	0.6239	0.057*
C12	0.7393 (3)	0.8938 (3)	0.5241 (3)	0.0399 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0440 (4)	0.0327 (4)	0.0669 (5)	0.0023 (3)	0.0113 (3)	0.0090 (3)
O1	0.0525 (11)	0.0270 (9)	0.0719 (13)	0.0066 (8)	0.0125 (9)	0.0076 (9)
N1	0.0416 (12)	0.0317 (11)	0.0496 (13)	0.0072 (9)	0.0078 (10)	0.0080 (10)
N2	0.0430 (12)	0.0269 (10)	0.0518 (13)	0.0043 (8)	0.0119 (10)	0.0122 (10)
C1	0.0548 (19)	0.0368 (16)	0.125 (3)	0.0045 (14)	0.0134 (19)	0.0060 (18)
C2	0.0361 (14)	0.0315 (14)	0.071 (2)	0.0091 (11)	0.0085 (13)	0.0047 (14)
C3	0.0553 (17)	0.0445 (16)	0.076 (2)	0.0150 (13)	0.0086 (15)	0.0258 (16)
C4	0.0546 (16)	0.0413 (15)	0.0446 (16)	0.0119 (12)	0.0002 (12)	0.0094 (13)
C5	0.0353 (13)	0.0336 (13)	0.0439 (15)	0.0107 (10)	0.0076 (11)	0.0081 (12)
C6	0.0384 (14)	0.0434 (15)	0.0439 (16)	0.0091 (11)	0.0055 (11)	0.0108 (13)
C7	0.0403 (15)	0.0465 (16)	0.0502 (17)	0.0053 (12)	0.0024 (12)	−0.0023 (14)
C8	0.075 (2)	0.075 (2)	0.0517 (19)	0.0139 (17)	0.0047 (15)	0.0268 (17)
C9	0.0401 (13)	0.0299 (12)	0.0344 (13)	0.0056 (10)	0.0024 (10)	0.0110 (11)
C10	0.0406 (15)	0.0461 (15)	0.0656 (19)	0.0094 (12)	0.0104 (13)	0.0123 (14)
C11	0.0487 (15)	0.0364 (14)	0.0521 (17)	0.0107 (11)	0.0135 (12)	0.0112 (13)
C12	0.0425 (14)	0.0312 (13)	0.0440 (15)	0.0101 (11)	0.0042 (11)	0.0133 (12)

Geometric parameters (Å, º) top

S1—C9	1.754 (2)	C4—C5	1.381 (4)
S1—C10	1.798 (3)	C4—H4	0.9300
O1—C12	1.223 (3)	C5—C6	1.388 (3)
N1—C9	1.264 (3)	C6—C7	1.391 (3)
N1—C5	1.436 (3)	C6—C8	1.503 (4)
N2—C12	1.365 (3)	C7—H7	0.9300
N2—C9	1.400 (3)	C8—H8B	0.9600
N2—H2	0.8600	C8—H8C	0.9600
C1—C2	1.509 (3)	C8—H8A	0.9600
C1—H1A	0.9600	C10—C11	1.510 (3)
C1—H1B	0.9600	C10—H10B	0.9700
C1—H1C	0.9600	C10—H10A	0.9700
C2—C7	1.378 (4)	C11—C12	1.492 (3)
C2—C3	1.378 (4)	C11—H11B	0.9700
C3—C4	1.381 (3)	C11—H11A	0.9700
C3—H3	0.9300

C9—S1—C10	101.58 (11)	C2—C7—H7	118.2
C9—N1—C5	117.4 (2)	C6—C7—H7	118.2
C12—N2—C9	128.4 (2)	C6—C8—H8B	109.5
C12—N2—H2	115.8	C6—C8—H8C	109.5
C9—N2—H2	115.8	H8B—C8—H8C	109.5
C2—C1—H1A	109.5	C6—C8—H8A	109.5
C2—C1—H1B	109.5	H8B—C8—H8A	109.5
H1A—C1—H1B	109.5	H8C—C8—H8A	109.5
C2—C1—H1C	109.5	N1—C9—N2	117.8 (2)
H1A—C1—H1C	109.5	N1—C9—S1	123.15 (18)
H1B—C1—H1C	109.5	N2—C9—S1	119.04 (17)
C7—C2—C3	117.3 (2)	C11—C10—S1	111.74 (18)
C7—C2—C1	121.2 (3)	C11—C10—H10B	109.3
C3—C2—C1	121.5 (3)	S1—C10—H10B	109.3
C2—C3—C4	120.9 (3)	C11—C10—H10A	109.3
C2—C3—H3	119.6	S1—C10—H10A	109.3
C4—C3—H3	119.6	H10B—C10—H10A	107.9
C3—C4—C5	120.7 (3)	C12—C11—C10	112.6 (2)
C3—C4—H4	119.6	C12—C11—H11B	109.1
C5—C4—H4	119.6	C10—C11—H11B	109.1
C4—C5—C6	120.0 (2)	C12—C11—H11A	109.1
C4—C5—N1	118.3 (2)	C10—C11—H11A	109.1
C6—C5—N1	121.6 (2)	H11B—C11—H11A	107.8
C5—C6—C7	117.3 (3)	O1—C12—N2	120.2 (2)
C5—C6—C8	121.7 (2)	O1—C12—C11	122.0 (2)
C7—C6—C8	120.9 (2)	N2—C12—C11	117.8 (2)
C2—C7—C6	123.7 (3)

C7—C2—C3—C4	−0.1 (4)	C8—C6—C7—C2	−179.1 (2)
C1—C2—C3—C4	179.7 (3)	C5—N1—C9—N2	179.5 (2)
C2—C3—C4—C5	1.4 (4)	C5—N1—C9—S1	−1.1 (3)
C3—C4—C5—C6	−2.1 (4)	C12—N2—C9—N1	−156.8 (2)
C3—C4—C5—N1	−179.4 (2)	C12—N2—C9—S1	23.7 (3)
C9—N1—C5—C4	−94.8 (3)	C10—S1—C9—N1	−177.0 (2)
C9—N1—C5—C6	87.9 (3)	C10—S1—C9—N2	2.4 (2)
C4—C5—C6—C7	1.4 (4)	C9—S1—C10—C11	−41.6 (2)
N1—C5—C6—C7	178.6 (2)	S1—C10—C11—C12	62.2 (3)
C4—C5—C6—C8	−179.6 (2)	C9—N2—C12—O1	172.6 (2)
N1—C5—C6—C8	−2.4 (4)	C9—N2—C12—C11	−7.2 (4)
C3—C2—C7—C6	−0.6 (4)	C10—C11—C12—O1	141.7 (2)
C1—C2—C7—C6	179.6 (2)	C10—C11—C12—N2	−38.5 (3)
C5—C6—C7—C2	0.0 (4)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C2–C7 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.08	2.900 (3)	161
C1—H1C···Cg2ⁱⁱ	0.96	2.72	3.591 (3)	152

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₂OS
M_r	234.31
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.2325 (4), 9.2000 (7), 10.0513 (7)
α, β, γ (°)	114.184 (7), 94.647 (5), 97.910 (5)
V (Å³)	597.27 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.48 × 0.28 × 0.23

Data collection
Diffractometer	Oxford Diffraction Xcalibur Atlas Gemini ultra
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2008)
T_min, T_max	0.919, 0.944
No. of measured, independent and observed [I > 2σ(I)] reflections	4061, 2188, 1569
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.115, 1.06
No. of reflections	2188
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.28

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

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C2–C7 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.075	2.900 (3)	161
C1—H1C···Cg2ⁱⁱ	0.96	2.716	3.591 (3)	152

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

Acknowledgements

The authors thank the Natural Science Foundation of Zhejiang Province, China, for financial support (grant No. Y4080234).

References

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Mogilaiah, K., Reddy, P., Raghotham, R. & Babu, R. (1999). Indian J. Chem. Sect. B, 38, 495–500. Google Scholar
Oxford Diffraction (2008). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Schroth, W., Herrmann, J., Feustel, C., Schmidt, S. & Jamil, K. M. (1977). Arch. Pharm. 32, 461–465. CAS Google Scholar
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Turkevich, N. M., Kolosova, L. G., Boikiv, D. P., Avgustinovich, M. S. & Vyshemirskaya, L. D. (1977). Farm. Zh. Kiev, 5, 55–60. PubMed Google Scholar

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