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

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.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.039
• wR factor = 0.102
• Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N2     --  C4      ..       6.63 su
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595         18
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          4
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT127_ALERT_1_C Implicit Hall Symbol  Inconsistent with Explicit        P 1

Alert level G
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         10
            C3  -N2  -C4  -N3    177.00  2.00   1.555   1.555   1.555   1.555

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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≡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

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)

S2. 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.

S3. 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 U_iso(H) = 1.2U_eq(C, N).

Computing details

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

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

Crystal data

C4H5N3S	Z = 2
Mr = 127.18	F(000) = 130
Triclinic, P1	Dx = 1.495 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4556 (13) Å	Cell parameters from 916 reflections
b = 6.5584 (13) Å	θ = 3.1–27.4°
c = 6.7910 (14) Å	µ = 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) Å^3

Data collection

Rigaku Saturn diffractometer	968 independent reflections
Radiation source: rotating anode	865 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.039
ω scans	θmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −6→7
Tmin = 0.898, Tmax = 0.982	k = −7→6
1570 measured reflections	l = −8→7

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0574P)^2] where P = (Fo^2 + 2Fc^2)/3
968 reflections	(Δ/σ)max < 0.001
73 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.19920 (8)	0.40549 (8)	0.26592 (8)	0.0167 (3)
N1	0.4033 (3)	0.7184 (3)	0.2385 (3)	0.0161 (4)
H1C	0.5069	0.7914	0.2164	0.019*
N2	0.6225 (3)	0.4094 (3)	0.2613 (3)	0.0158 (5)
N3	0.6775 (3)	0.0290 (3)	0.2589 (3)	0.0234 (5)
C1	0.0574 (4)	0.6574 (3)	0.2008 (4)	0.0184 (5)
H1A	0.0483	0.6789	0.0584	0.022*
H1B	−0.0843	0.6700	0.2732	0.022*
C2	0.1853 (4)	0.8129 (3)	0.2610 (4)	0.0187 (5)
H2A	0.1700	0.9417	0.1752	0.022*
H2B	0.1384	0.8415	0.3985	0.022*
C3	0.4340 (4)	0.5138 (3)	0.2539 (3)	0.0139 (5)
C4	0.6407 (3)	0.2063 (3)	0.2601 (3)	0.0166 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0153 (4)	0.0143 (4)	0.0224 (4)	−0.0053 (2)	−0.0049 (2)	−0.0020 (2)
N1	0.0159 (10)	0.0126 (10)	0.0221 (11)	−0.0057 (7)	−0.0056 (8)	−0.0021 (7)
N2	0.0160 (10)	0.0118 (10)	0.0211 (11)	−0.0035 (7)	−0.0050 (8)	−0.0022 (7)
N3	0.0211 (11)	0.0139 (11)	0.0358 (13)	−0.0013 (8)	−0.0083 (9)	−0.0013 (8)
C1	0.0154 (11)	0.0183 (12)	0.0227 (13)	−0.0004 (9)	−0.0065 (9)	−0.0034 (9)
C2	0.0200 (12)	0.0145 (12)	0.0221 (13)	−0.0003 (9)	−0.0050 (9)	−0.0039 (9)
C3	0.0192 (11)	0.0144 (11)	0.0096 (11)	−0.0054 (9)	−0.0031 (9)	−0.0018 (8)
C4	0.0126 (11)	0.0220 (13)	0.0166 (12)	−0.0041 (9)	−0.0053 (9)	−0.0008 (9)

Geometric parameters (Å, º)

S1—C3	1.747 (2)	N3—C4	1.155 (3)
S1—C1	1.816 (2)	C1—C2	1.522 (3)
N1—C3	1.323 (3)	C1—H1A	0.9700
N1—C2	1.452 (3)	C1—H1B	0.9700
N1—H1C	0.8600	C2—H2A	0.9700
N2—C3	1.317 (3)	C2—H2B	0.9700
N2—C4	1.321 (3)
C3—S1—C1	91.15 (10)	N1—C2—C1	106.10 (17)
C3—N1—C2	116.32 (19)	N1—C2—H2A	110.5
C3—N1—H1C	121.8	C1—C2—H2A	110.5
C2—N1—H1C	121.8	N1—C2—H2B	110.5
C3—N2—C4	117.9 (2)	C1—C2—H2B	110.5
C2—C1—S1	105.21 (16)	H2A—C2—H2B	108.7
C2—C1—H1A	110.7	N2—C3—N1	122.1 (2)
S1—C1—H1A	110.7	N2—C3—S1	125.53 (17)
C2—C1—H1B	110.7	N1—C3—S1	112.34 (17)
S1—C1—H1B	110.7	N3—C4—N2	173.3 (2)
H1A—C1—H1B	108.8
C3—S1—C1—C2	−23.42 (16)	C2—N1—C3—N2	−171.4 (2)
C3—N1—C2—C1	−25.8 (3)	C2—N1—C3—S1	7.9 (2)
S1—C1—C2—N1	30.4 (2)	C1—S1—C3—N2	−170.6 (2)
C4—N2—C3—N1	−174.6 (2)	C1—S1—C3—N1	10.19 (17)
C4—N2—C3—S1	6.3 (3)	C3—N2—C4—N3	177 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···N3^i	0.86	2.10	2.903 (3)	156

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