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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o2148.
Published online 2010 July 31. doi:  10.1107/S160053681002917X
PMCID: PMC3007512

(Z)-2-(1,3-Thia­zolidin-2-yl­idene)cyan­amide

Abstract

In the title compound, C4H5N3S, the tdihydrothiazole ring is almost planar, the maximum and minimum deviations being 0.188 (2) Å and 0.042 (3) Å, respectively. The crystal structure involves intermolecular N—H(...)N hydrogen bonds.

Related literature

The title compound was synthesized as an inter­mediate for the synthesis of nicotine insecticides. For their biological activity and synthetic information, see: Jeschke et al. (2002 [triangle]); Hense et al. (2002 [triangle]). For a related structure, see: Dupont et al. (1995 [triangle]). For typical triple-bond lengths, see: Allen et al. (1987 [triangle])

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Object name is e-66-o2148-scheme1.jpg

Experimental

Crystal data

  • C4H5N3S
  • M r = 127.18
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2148-efi1.jpg
  • a = 6.4556 (13) Å
  • b = 6.5584 (13) Å
  • c = 6.7910 (14) Å
  • α = 83.28 (3)°
  • β = 81.53 (3)°
  • γ = 82.12 (3)°
  • V = 280.32 (10) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.46 mm−1
  • T = 113 K
  • 0.24 × 0.18 × 0.04 mm

Data collection

  • Rigaku Saturn diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.898, T max = 0.982
  • 1570 measured reflections
  • 968 independent reflections
  • 865 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.102
  • S = 1.06
  • 968 reflections
  • 73 parameters
  • H-atom parameters constrained
  • Δρmax = 0.38 e Å−3
  • Δρmin = −0.37 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); 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/S160053681002917X/bv2145sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681002917X/bv2145Isup2.hkl

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

supplementary crystallographic information

Comment

Many nicotine insecticide derivatives have been reported showing various biological activities, e.g. thiacloprid (Jeschke et al., 2002). The title compound (I) was synthesized as an intermediate for the synthesis of nicotine insecticides (Hense et al., 2002). As an important intermediate for the syntesis of insecticides, we report here the crystal structure of (I).

In (I) (Fig. 1), main bond (C—C,C—N,S—C) lengths are normal and in a good agreement with those reported previously (Dupont et al., 1995). Torsion angles of the thiazole ring are small [C4—N2—C3—S1, 6.52 (3)°, C1—S1—C3—N1, 9.95 (2)° and C2—N1—C3—S1, 7.98 (3)°] and thiazole ring is almost planar as the maximum and minimum deviations are 0.188Å and 0.042Å respectively. In the thiazole ring, the dihedral angle between plane A (C1/C2/C3/C4) and plane B (S1/N1/N2/C3) is 5.5 (3)°. The molecule contains a nitrile group, with an C[equivalent]N distance of 1.158 (1) Å, which indicates substantial triple bond character (Allen et al., 1987). Recently, compounds containing the thiazolidin-2-yl-cyanamide group have attracted much interest because compounds containing a thiazole ring system are well known as efficient insecticides (Hense, et al., 2002). The structure is stabilized by hydrogen bonds of N—H···N type.

Experimental

Cyano-dimethyl dithiocarbamate 14.6 g (0.1 mol) was dissolved in 35 ml ethanol with stirrer and 2-amino-ethanethiol 11.4 g (0.1 mol) was slowly added to the mixture while maintaining the temperature at 303–313 K. After three hours, ethanol was removed under reduced pressure to give title compounds 11.2 g, yield 88%. (Jeschke, et al.,2002). Single crystals suitable for X-ray measurement were obtained by recrystallization from the mixture of acetone and methanol at room temperature.

Refinement

All H atoms were placed in calculated positions, with C—H = 0.97 Å and N—H = 0.86 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq(C, N).

Figures

Fig. 1.
View of the title compound (I), with displacement ellipsoids drawn at the 40% probability level.

Crystal data

C4H5N3SZ = 2
Mr = 127.18F(000) = 130
Triclinic, P1Dx = 1.495 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.4556 (13) ÅCell parameters from 916 reflections
b = 6.5584 (13) Åθ = 3.1–27.4°
c = 6.7910 (14) ŵ = 0.46 mm1
α = 83.28 (3)°T = 113 K
β = 81.53 (3)°Prism, colorless
γ = 82.12 (3)°0.24 × 0.18 × 0.04 mm
V = 280.32 (10) Å3

Data collection

Rigaku Saturn diffractometer968 independent reflections
Radiation source: rotating anode865 reflections with I > 2σ(I)
confocalRint = 0.039
ω scansθmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)h = −6→7
Tmin = 0.898, Tmax = 0.982k = −7→6
1570 measured reflectionsl = −8→7

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.0574P)2] where P = (Fo2 + 2Fc2)/3
968 reflections(Δ/σ)max < 0.001
73 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = −0.36 e Å3

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
S10.19920 (8)0.40549 (8)0.26592 (8)0.0167 (3)
N10.4033 (3)0.7184 (3)0.2385 (3)0.0161 (4)
H1C0.50690.79140.21640.019*
N20.6225 (3)0.4094 (3)0.2613 (3)0.0158 (5)
N30.6775 (3)0.0290 (3)0.2589 (3)0.0234 (5)
C10.0574 (4)0.6574 (3)0.2008 (4)0.0184 (5)
H1A0.04830.67890.05840.022*
H1B−0.08430.67000.27320.022*
C20.1853 (4)0.8129 (3)0.2610 (4)0.0187 (5)
H2A0.17000.94170.17520.022*
H2B0.13840.84150.39850.022*
C30.4340 (4)0.5138 (3)0.2539 (3)0.0139 (5)
C40.6407 (3)0.2063 (3)0.2601 (3)0.0166 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0153 (4)0.0143 (4)0.0224 (4)−0.0053 (2)−0.0049 (2)−0.0020 (2)
N10.0159 (10)0.0126 (10)0.0221 (11)−0.0057 (7)−0.0056 (8)−0.0021 (7)
N20.0160 (10)0.0118 (10)0.0211 (11)−0.0035 (7)−0.0050 (8)−0.0022 (7)
N30.0211 (11)0.0139 (11)0.0358 (13)−0.0013 (8)−0.0083 (9)−0.0013 (8)
C10.0154 (11)0.0183 (12)0.0227 (13)−0.0004 (9)−0.0065 (9)−0.0034 (9)
C20.0200 (12)0.0145 (12)0.0221 (13)−0.0003 (9)−0.0050 (9)−0.0039 (9)
C30.0192 (11)0.0144 (11)0.0096 (11)−0.0054 (9)−0.0031 (9)−0.0018 (8)
C40.0126 (11)0.0220 (13)0.0166 (12)−0.0041 (9)−0.0053 (9)−0.0008 (9)

Geometric parameters (Å, °)

S1—C31.747 (2)N3—C41.155 (3)
S1—C11.816 (2)C1—C21.522 (3)
N1—C31.323 (3)C1—H1A0.9700
N1—C21.452 (3)C1—H1B0.9700
N1—H1C0.8600C2—H2A0.9700
N2—C31.317 (3)C2—H2B0.9700
N2—C41.321 (3)
C3—S1—C191.15 (10)N1—C2—C1106.10 (17)
C3—N1—C2116.32 (19)N1—C2—H2A110.5
C3—N1—H1C121.8C1—C2—H2A110.5
C2—N1—H1C121.8N1—C2—H2B110.5
C3—N2—C4117.9 (2)C1—C2—H2B110.5
C2—C1—S1105.21 (16)H2A—C2—H2B108.7
C2—C1—H1A110.7N2—C3—N1122.1 (2)
S1—C1—H1A110.7N2—C3—S1125.53 (17)
C2—C1—H1B110.7N1—C3—S1112.34 (17)
S1—C1—H1B110.7N3—C4—N2173.3 (2)
H1A—C1—H1B108.8
C3—S1—C1—C2−23.42 (16)C2—N1—C3—N2−171.4 (2)
C3—N1—C2—C1−25.8 (3)C2—N1—C3—S17.9 (2)
S1—C1—C2—N130.4 (2)C1—S1—C3—N2−170.6 (2)
C4—N2—C3—N1−174.6 (2)C1—S1—C3—N110.19 (17)
C4—N2—C3—S16.3 (3)C3—N2—C4—N3177 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1C···N3i0.862.102.903 (3)156

Symmetry codes: (i) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BV2145).

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.
  • Dupont, L., Masereel, B., Lambert, D. & Scriba, G. (1995). Acta Cryst. C51, 1901–1903.
  • Hense, A., Fischer. Gesing, E. R. (2002). WO Patent 2002096872.
  • Jeschke, P., Beck, M. E. & Kraemer, W. (2002). DE Patent 10119423.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography