(Z)-(1,3-Thia­zinan-2-ylideneamino)formo­nitrile

Peng, Y.; Wu, L.

doi:10.1107/S1600536809008940

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o784

doi:10.1107/S1600536809008940

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(Z)-(1,3-Thiazinan-2-ylideneamino)formonitrile

Yu-wen Peng ^a ^* and Lin-hai Wu ^b

^aJiang Nan University, Wu-Xi 214112, People's Republic of China, and, Finance Department of Business School, Hunan Normal University, Changsha 412006, People's Republic of China, and ^bJiang Nan University, Wu-Xi 214112, People's Republic of China;
^*Correspondence e-mail: pyw123456@tom.com

(Received 9 March 2009; accepted 11 March 2009; online 19 March 2009)

In the title molecule, C₅H₇N₃S, the thiazine ring shows a conformation close to a half-boat. The Cremer & Pople puckering parameters of the thiazine ring are q2 = 0.4645 (2) Å, θ = 132.4 (3) and φ = 285.52 (2)°. The packing is stabilized by intermolecular N—H⋯N and C—H⋯S interactions.

Related literature

For the crystal structures of thiazine compounds, see: Kálmán, et al. (1977 ). For the biological activities of thiazine-containing compounds, see: Soloway et al. (1978 ); Tomizawa et al. (1995 ). For bond-length data, see: Allen et al. (1987 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₅H₇N₃S
M_r = 141.21
Monoclinic, P 2₁ /c
a = 7.0931 (14) Å
b = 12.689 (3) Å
c = 9.232 (3) Å
β = 128.617 (19)°
V = 649.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 153 K
0.42 × 0.11 × 0.06 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi 1995 ) T_min = 0.849, T_max = 0.976
4731 measured reflections
1101 independent reflections
970 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.192
S = 1.09
1101 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 1.14 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
N1—H1A⋯N3ⁱ	0.86	2.12	2.926 (4)	156
C3—H3B⋯S1ⁱⁱ	0.99	2.74	3.468 (3)	131
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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/S1600536809008940/hg2486sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008940/hg2486Isup2.hkl

checkCIF report

Comment top

The frequent occurence of pesticide residues accidents and the introduction of Green Trade Barriers to protect human health threaten export and national agriculture market and highlights the importance of food safely. Therefore, the development of pesticides with new chemical structures and high insecticidal activities with low residues is highly desirable. Consequently, spurred by the need for new pesticidal agents and the fact that many new effective pesticides possess heterocyclic rings in their structure, such as the thiazine ring (Soloway et al., 1978; Tomizawa et al., 1995), over the last few years, we have synthesized some novel thiazine derivatives. Here, we report the crystal structure of (Z)-(1,3-thiazinan-2-ylideneamino)formonitrile.

In (Z)-(1,3-thiazinan-2-ylideneamino)formonitrile (Fig. 1), all bond lengths are normal (Allen et al., 1987) and in a good agreement with those reported previously (Kálmán, et al., 1977). It is known that the imino tautomers can exist as two geometrical isomers, syn (Z) and anti (E), but in this crystal, only Z isomers have been observed. The thiazine ring shows a conformation near to half boat with the C2 atom deviating 0.618 (2) Å above the plane formed by S1, C1, N1, C3 and C4 [maximum least squares plane deviation for S1 0.053 (3) Å]. This geometry is proved by the puckering parameters q2 = 0.4645 (2) Å, θ = 132.4 (3)° and ϕ = 285.52 (2)° (Cremer & Pople, 1975). There are some weak N—H···N and C—H···S intermolecular interactions (see Table 1) which stabilize the title structure.

Related literature top

For the crystal structures of thiazine compounds, see: Kálmán, et al. (1977). For the biological activities of thiazine-containing compounds, see: Soloway et al. (1978); Tomizawa et al. (1995). For bond-length data, see: Allen et al. (1987). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

A mixture of dimethyl cyanocarbonimidodithioate 10 mmol (1.46 g) and 3-aminopropane-1-thiol (1.00 g, 11 mmol) was refluxed in absolute EtOH (20 ml) for 3 h. On cooling, the product crystallizes and was filtered and then recrystallized from absolute ethanol. Yield 1.20 g (85%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); 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 atom labels and 40% probability displacement ellipsoids for non-H atoms.

(Z)-(1,3-Thiazinan-2-ylideneamino)formonitrile top

Crystal data top

C₅H₇N₃S	F(000) = 296
M_r = 141.21	D_x = 1.445 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2501 reflections
a = 7.0931 (14) Å	θ = 2.3–25.1°
b = 12.689 (3) Å	µ = 0.40 mm⁻¹
c = 9.232 (3) Å	T = 153 K
β = 128.617 (19)°	Needle, colorless
V = 649.2 (3) Å³	0.42 × 0.11 × 0.06 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	1101 independent reflections
Radiation source: Rotating Anode	970 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω Oscillation scans	θ_max = 25.0°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi 1995)	h = −8→8
T_min = 0.849, T_max = 0.976	k = −14→15
4731 measured reflections	l = −10→10

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)] = 0.066	H-atom parameters constrained
wR(F²) = 0.192	w = 1/[σ²(F_o²) + (0.1515P)² + 0.068P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
1101 reflections	Δρ_max = 1.14 e Å⁻³
83 parameters	Δρ_min = −0.32 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: 0.040 (14)

Crystal data top

C₅H₇N₃S	V = 649.2 (3) Å³
M_r = 141.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.0931 (14) Å	µ = 0.40 mm⁻¹
b = 12.689 (3) Å	T = 153 K
c = 9.232 (3) Å	0.42 × 0.11 × 0.06 mm
β = 128.617 (19)°

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	1101 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi 1995)	970 reflections with I > 2σ(I)
T_min = 0.849, T_max = 0.976	R_int = 0.032
4731 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.192	H-atom parameters constrained
S = 1.09	Δρ_max = 1.14 e Å⁻³
1101 reflections	Δρ_min = −0.32 e Å⁻³
83 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	0.97192 (13)	0.28689 (6)	0.64894 (10)	0.0263 (5)
N1	0.7395 (4)	0.47140 (17)	0.5152 (3)	0.0213 (6)
H1A	0.6246	0.5077	0.4223	0.026*
N2	0.5695 (4)	0.33420 (19)	0.3151 (3)	0.0231 (7)
N3	0.5490 (5)	0.1469 (2)	0.2340 (4)	0.0324 (8)
C1	1.1467 (7)	0.3667 (3)	0.8561 (5)	0.0406 (10)
H1B	1.0764	0.3613	0.9206	0.049*
H1C	1.3136	0.3390	0.9404	0.049*
C2	1.1539 (7)	0.4785 (3)	0.8161 (5)	0.0403 (9)
H2B	1.2330	0.4840	0.7582	0.048*
H2C	1.2538	0.5179	0.9345	0.048*
C3	0.9066 (6)	0.5297 (3)	0.6889 (5)	0.0316 (8)
H3A	0.8374	0.5342	0.7544	0.038*
H3B	0.9245	0.6023	0.6600	0.038*
C4	0.7430 (5)	0.3711 (2)	0.4833 (4)	0.0189 (7)
C5	0.5676 (5)	0.2335 (2)	0.2802 (4)	0.0228 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0269 (6)	0.0189 (6)	0.0199 (6)	0.0071 (3)	0.0081 (5)	0.0043 (2)
N1	0.0262 (13)	0.0119 (11)	0.0189 (13)	0.0008 (10)	0.0108 (12)	−0.0002 (9)
N2	0.0243 (13)	0.0159 (13)	0.0174 (13)	0.0017 (10)	0.0073 (11)	−0.0020 (9)
N3	0.0362 (17)	0.0226 (15)	0.0376 (18)	−0.0079 (12)	0.0226 (15)	−0.0118 (12)
C1	0.0317 (19)	0.052 (2)	0.0163 (17)	0.0024 (15)	0.0041 (15)	−0.0040 (14)
C2	0.040 (2)	0.044 (2)	0.032 (2)	−0.0136 (16)	0.0198 (18)	−0.0108 (15)
C3	0.0365 (19)	0.0224 (16)	0.0284 (18)	−0.0043 (14)	0.0165 (16)	−0.0111 (13)
C4	0.0206 (14)	0.0179 (14)	0.0165 (15)	0.0000 (11)	0.0107 (13)	0.0014 (11)
C5	0.0180 (14)	0.0265 (16)	0.0181 (15)	−0.0046 (12)	0.0085 (13)	−0.0056 (12)

Geometric parameters (Å, º) top

S1—C4	1.737 (3)	C1—C2	1.474 (6)
S1—C1	1.806 (4)	C1—H1B	0.9900
N1—C4	1.310 (4)	C1—H1C	0.9900
N1—C3	1.467 (4)	C2—C3	1.519 (5)
N1—H1A	0.8600	C2—H2B	0.9900
N2—C5	1.315 (4)	C2—H2C	0.9900
N2—C4	1.327 (4)	C3—H3A	0.9900
N3—C5	1.156 (4)	C3—H3B	0.9900

C4—S1—C1	103.52 (16)	C1—C2—H2C	108.8
C4—N1—C3	128.3 (3)	C3—C2—H2C	108.8
C4—N1—H1A	115.8	H2B—C2—H2C	107.7
C3—N1—H1A	115.9	N1—C3—C2	112.6 (3)
C5—N2—C4	119.3 (2)	N1—C3—H3A	109.1
C2—C1—S1	112.5 (3)	C2—C3—H3A	109.1
C2—C1—H1B	109.1	N1—C3—H3B	109.1
S1—C1—H1B	109.1	C2—C3—H3B	109.1
C2—C1—H1C	109.1	H3A—C3—H3B	107.8
S1—C1—H1C	109.1	N1—C4—N2	118.2 (3)
H1B—C1—H1C	107.8	N1—C4—S1	122.6 (2)
C1—C2—C3	113.7 (3)	N2—C4—S1	119.2 (2)
C1—C2—H2B	108.8	N3—C5—N2	174.2 (3)
C3—C2—H2B	108.8

C4—S1—C1—C2	−34.3 (3)	C5—N2—C4—N1	−179.3 (3)
S1—C1—C2—C3	59.4 (4)	C5—N2—C4—S1	3.5 (4)
C4—N1—C3—C2	25.2 (4)	C1—S1—C4—N1	7.7 (3)
C1—C2—C3—N1	−54.0 (4)	C1—S1—C4—N2	−175.3 (2)
C3—N1—C4—N2	178.6 (3)	C4—N2—C5—N3	−177 (3)
C3—N1—C4—S1	−4.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N3ⁱ	0.86	2.12	2.926 (4)	156
C3—H3B···S1ⁱⁱ	0.99	2.74	3.468 (3)	131

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₅H₇N₃S
M_r	141.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	153
a, b, c (Å)	7.0931 (14), 12.689 (3), 9.232 (3)
β (°)	128.617 (19)
V (Å³)	649.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.42 × 0.11 × 0.06

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi 1995)
T_min, T_max	0.849, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	4731, 1101, 970
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.192, 1.09
No. of reflections	1101
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.14, −0.32

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N3ⁱ	0.86	2.12	2.926 (4)	155.6
C3—H3B···S1ⁱⁱ	0.99	2.74	3.468 (3)	130.5

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+2, y+1/2, −z+3/2.

Acknowledgements

We gratefully acknowledge Dr Jing-Kun Xu for valuable advice given by him in the preparation of the reported compound.

References

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