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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o784.
Published online 2009 March 19. doi:  10.1107/S1600536809008940
PMCID: PMC2968830

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

Abstract

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

An external file that holds a picture, illustration, etc.
Object name is e-65-0o784-scheme1.jpg

Experimental

Crystal data

  • C5H7N3S
  • M r = 141.21
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o784-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.066
  • wR(F 2) = 0.192
  • S = 1.09
  • 1101 reflections
  • 83 parameters
  • H-atom parameters constrained
  • Δρmax = 1.14 e Å−3
  • Δρmin = −0.32 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2004 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809008940/hg2486sup1.cif

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

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

Acknowledgments

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

supplementary crystallographic information

Comment

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 [var phi] = 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.

Experimental

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.

Refinement

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.99 Å, N—H = 0.86 Å with Uiso(H) = 1.2 times Ueq(C, N).

Figures

Fig. 1.
The molecular structure of (I), with atom labels and 40% probability displacement ellipsoids for non-H atoms.

Crystal data

C5H7N3SF(000) = 296
Mr = 141.21Dx = 1.445 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2501 reflections
a = 7.0931 (14) Åθ = 2.3–25.1°
b = 12.689 (3) ŵ = 0.40 mm1
c = 9.232 (3) ÅT = 153 K
β = 128.617 (19)°Needle, colorless
V = 649.2 (3) Å30.42 × 0.11 × 0.06 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer1101 independent reflections
Radiation source: Rotating Anode970 reflections with I > 2σ(I)
graphiteRint = 0.032
ω Oscillation scansθmax = 25.0°, θmin = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi 1995)h = −8→8
Tmin = 0.849, Tmax = 0.976k = −14→15
4731 measured reflectionsl = −10→10

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.066H-atom parameters constrained
wR(F2) = 0.192w = 1/[σ2(Fo2) + (0.1515P)2 + 0.068P] where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
1101 reflectionsΔρmax = 1.14 e Å3
83 parametersΔρmin = −0.31 e Å3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.040 (14)

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 (Å2)

xyzUiso*/Ueq
S10.97192 (13)0.28689 (6)0.64894 (10)0.0263 (5)
N10.7395 (4)0.47140 (17)0.5152 (3)0.0213 (6)
H1A0.62460.50770.42230.026*
N20.5695 (4)0.33420 (19)0.3151 (3)0.0231 (7)
N30.5490 (5)0.1469 (2)0.2340 (4)0.0324 (8)
C11.1467 (7)0.3667 (3)0.8561 (5)0.0406 (10)
H1B1.07640.36130.92060.049*
H1C1.31360.33900.94040.049*
C21.1539 (7)0.4785 (3)0.8161 (5)0.0403 (9)
H2B1.23300.48400.75820.048*
H2C1.25380.51790.93450.048*
C30.9066 (6)0.5297 (3)0.6889 (5)0.0316 (8)
H3A0.83740.53420.75440.038*
H3B0.92450.60230.66000.038*
C40.7430 (5)0.3711 (2)0.4833 (4)0.0189 (7)
C50.5676 (5)0.2335 (2)0.2802 (4)0.0228 (7)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0269 (6)0.0189 (6)0.0199 (6)0.0071 (3)0.0081 (5)0.0043 (2)
N10.0262 (13)0.0119 (11)0.0189 (13)0.0008 (10)0.0108 (12)−0.0002 (9)
N20.0243 (13)0.0159 (13)0.0174 (13)0.0017 (10)0.0073 (11)−0.0020 (9)
N30.0362 (17)0.0226 (15)0.0376 (18)−0.0079 (12)0.0226 (15)−0.0118 (12)
C10.0317 (19)0.052 (2)0.0163 (17)0.0024 (15)0.0041 (15)−0.0040 (14)
C20.040 (2)0.044 (2)0.032 (2)−0.0136 (16)0.0198 (18)−0.0108 (15)
C30.0365 (19)0.0224 (16)0.0284 (18)−0.0043 (14)0.0165 (16)−0.0111 (13)
C40.0206 (14)0.0179 (14)0.0165 (15)0.0000 (11)0.0107 (13)0.0014 (11)
C50.0180 (14)0.0265 (16)0.0181 (15)−0.0046 (12)0.0085 (13)−0.0056 (12)

Geometric parameters (Å, °)

S1—C41.737 (3)C1—C21.474 (6)
S1—C11.806 (4)C1—H1B0.9900
N1—C41.310 (4)C1—H1C0.9900
N1—C31.467 (4)C2—C31.519 (5)
N1—H1A0.8600C2—H2B0.9900
N2—C51.315 (4)C2—H2C0.9900
N2—C41.327 (4)C3—H3A0.9900
N3—C51.156 (4)C3—H3B0.9900
C4—S1—C1103.52 (16)C1—C2—H2C108.8
C4—N1—C3128.3 (3)C3—C2—H2C108.8
C4—N1—H1A115.8H2B—C2—H2C107.7
C3—N1—H1A115.9N1—C3—C2112.6 (3)
C5—N2—C4119.3 (2)N1—C3—H3A109.1
C2—C1—S1112.5 (3)C2—C3—H3A109.1
C2—C1—H1B109.1N1—C3—H3B109.1
S1—C1—H1B109.1C2—C3—H3B109.1
C2—C1—H1C109.1H3A—C3—H3B107.8
S1—C1—H1C109.1N1—C4—N2118.2 (3)
H1B—C1—H1C107.8N1—C4—S1122.6 (2)
C1—C2—C3113.7 (3)N2—C4—S1119.2 (2)
C1—C2—H2B108.8N3—C5—N2174.2 (3)
C3—C2—H2B108.8
C4—S1—C1—C2−34.3 (3)C5—N2—C4—N1−179.3 (3)
S1—C1—C2—C359.4 (4)C5—N2—C4—S13.5 (4)
C4—N1—C3—C225.2 (4)C1—S1—C4—N17.7 (3)
C1—C2—C3—N1−54.0 (4)C1—S1—C4—N2−175.3 (2)
C3—N1—C4—N2178.6 (3)C4—N2—C5—N3−177 (3)
C3—N1—C4—S1−4.3 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···N3i0.862.122.926 (4)156
C3—H3B···S1ii0.992.743.468 (3)131

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2486).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Kálmán, A., Argay, G., Riba’r, B. & Toldy, L. (1977). Tetrahedron Lett.48, 4241–4244.
  • Rigaku (2004). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • 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 and T. Smyth, pp. 153–158. New York: Plenum Press.
  • Tomizawa, M., Otsuka, H., Miyamoto, T. & Yamamoto, I. (1995). J. Pestic. Sci. 20, 49–56.

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