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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 8| August 2010| Page o2148
https://doi.org/10.1107/S160053681002917X

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

Xiao-tao Chena and Liang-zhong Xua*

aCollege of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China
*Correspondence e-mail: qknhs@yahoo.com.cn

(Received 24 May 2010; accepted 22 July 2010; online 31 July 2010)

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[Jeschke, P., Beck, M. E. & Kraemer, W. (2002). DE Patent 10119423.]); Hense et al. (2002[Hense, A., Fischer. Gesing, E. R. (2002). WO Patent 2002096872.]). For a related structure, see: Dupont et al. (1995[Dupont, L., Masereel, B., Lambert, D. & Scriba, G. (1995). Acta Cryst. C51, 1901-1903.]). For typical triple-bond lengths, see: Allen et al. (1987[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.])

[Scheme 1]

Experimental

Crystal data

  • C4H5N3S

  • Mr = 127.18

  • Triclinic, [P \overline 1]

  • 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.898, Tmax = 0.982

  • 1570 measured reflections

  • 968 independent reflections

  • 865 reflections with I > 2σ(I)

  • Rint = 0.039
Refinement

  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1C⋯N3i 0.86 2.10 2.903 (3) 156
Symmetry code: (i) x, y+1, z.

Data collection: CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681002917X/bv2145sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681002917X/bv2145Isup2.hkl

checkCIF report


Comment top

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≡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.

Related literature top

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); Hense et al. (2002). For a related structure, see: Dupont et al. (1995). For typical triple-bond lengths, see: Allen et al. (1987)

Experimental top

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 top

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).

Structure description top

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≡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.

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); Hense et al. (2002). For a related structure, see: Dupont et al. (1995). For typical triple-bond lengths, see: Allen et al. (1987)

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. View of the title compound (I), with displacement ellipsoids drawn at the 40% probability level.
(Z)-2-(1,3-Thiazolidin-2-ylidene)cyanamide top
Crystal data top
C4H5N3SZ = 2
Mr = 127.18F(000) = 130
Triclinic, P1Dx = 1.495 Mg m−3
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 mm−1
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 top
Rigaku Saturn
diffractometer		968 independent reflections
Radiation source: rotating anode865 reflections with I > 2σ(I)
Confocal monochromatorRint = 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 top
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 = 1.06 w = 1/[σ2(Fo2) + (0.0574P)2]
where P = (Fo2 + 2Fc2)/3
968 reflections(Δ/σ)max < 0.001
73 parametersΔρmax = 0.38 e Å−3
0 restraintsΔρmin = −0.37 e Å−3
Crystal data top
C4H5N3Sγ = 82.12 (3)°
Mr = 127.18V = 280.32 (10) Å3
Triclinic, P1Z = 2
a = 6.4556 (13) ÅMo Kα radiation
b = 6.5584 (13) ŵ = 0.46 mm−1
c = 6.7910 (14) ÅT = 113 K
α = 83.28 (3)°0.24 × 0.18 × 0.04 mm
β = 81.53 (3)°
Data collection top
Rigaku Saturn
diffractometer		968 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		865 reflections with I > 2σ(I)
Tmin = 0.898, Tmax = 0.982Rint = 0.039
1570 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.102H-atom parameters constrained
S = 1.06Δρmax = 0.38 e Å−3
968 reflectionsΔρmin = −0.37 e Å−3
73 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
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) top
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, º) top
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, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···N3i0.862.102.903 (3)156
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC4H5N3S
Mr127.18
Crystal system, space groupTriclinic, P1
Temperature (K)113
a, b, c (Å)6.4556 (13), 6.5584 (13), 6.7910 (14)
α, β, γ (°)83.28 (3), 81.53 (3), 82.12 (3)
V (Å3)280.32 (10)
Z2
Radiation typeMo Kα
µ (mm−1)0.46
Crystal size (mm)0.24 × 0.18 × 0.04
Data collection
DiffractometerRigaku Saturn
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.898, 0.982
No. of measured, independent and
observed [I > 2σ(I)] reflections		1570, 968, 865
Rint0.039
(sin θ/λ)max (Å−1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.102, 1.06
No. of reflections968
No. of parameters73
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.38, −0.37

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···N3i0.862.102.903 (3)156.0
Symmetry code: (i) x, y+1, z.
 

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CSD CrossRef Web of Science Google Scholar
 First citationDupont, L., Masereel, B., Lambert, D. & Scriba, G. (1995). Acta Cryst. C51, 1901–1903.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
 First citationHense, A., Fischer. Gesing, E. R. (2002). WO Patent 2002096872.  Google Scholar
 First citationJeschke, P., Beck, M. E. & Kraemer, W. (2002). DE Patent 10119423.  Google Scholar
 First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 8| August 2010| Page o2148
https://doi.org/10.1107/S160053681002917X
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