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Acta Crystallogr Sect E Struct Rep Online. 2010 March 1; 66(Pt 3): o604.
Published online 2010 February 13. doi:  10.1107/S1600536810004915
PMCID: PMC2983548

(E)-1-[(2-Chloro-5-methyl­pyridin-3-yl)methyl­ene]thiosemicarbazide

Abstract

The title compound, C8H9ClN4S, which has potential insecticidal activity, was synthesized by the reaction of 2-chloro-5-methyl­nicotinaldehyde and thio­semicarbazide. In the crystal structure, the mol­ecules are linked via inter­molecular N—H(...)N, N—H(...)S and N—H(...)Cl hydrogen bonds, forming a three-dimensional network stacked down a.

Related literature

Tyrosinase is a key enzyme in the moulting process of insects, see: Kramer & Knost (2001 [triangle]). For the inhibitory activity on tyrosinase of benzaldehyde thio­semi­carbazones, see: Xue et al. (2007 [triangle]). For the synthesis of the title compound, see: Liu et al. (2008 [triangle]).

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Object name is e-66-0o604-scheme1.jpg

Experimental

Crystal data

  • C8H9ClN4S
  • M r = 228.70
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o604-efi1.jpg
  • a = 8.776 (3) Å
  • b = 15.523 (4) Å
  • c = 7.540 (2) Å
  • β = 96.193 (16)°
  • V = 1021.2 (5) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 4.95 mm−1
  • T = 173 K
  • 0.45 × 0.30 × 0.30 mm

Data collection

  • Rigaku R-AXIS Rapid diffractometer
  • Absorption correction: numerical (ABSCOR; Higashi, 1995 [triangle]) T min = 0.214, T max = 0.319
  • 6565 measured reflections
  • 1847 independent reflections
  • 1598 reflections with I > 2σ(I)
  • R int = 0.048

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.105
  • S = 1.11
  • 1847 reflections
  • 129 parameters
  • H-atom parameters constrained
  • Δρmax = 0.27 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2001 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP in SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536810004915/ds2018sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004915/ds2018Isup2.hkl

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

Acknowledgments

This work was supported by the National High Technology Research and Development Program of China (2006 A A10A201). We acknowledge Dr Liang Tongling for collecting the data at the Analysis and Testing Center, Institute of Chemistry Academy of Science, Beijing.

supplementary crystallographic information

Comment

Tyrosinase is a key enzyme in the molting process of insect (Kramer & Knost 2001), and benzaldehyde thiosemicarbazones have inhibitory activity on tyrosinase (Xue et al., 2007). In order to look for highly potent tyrosinase inhibitors, the title compound was synthesized by the reaction of thiosemicarbazide and 2-chloro-5-methylnicotinaldehyde (Liu et al., 2008). Finally in the preliminary bioassay, we found that it showed obvious inhibitory activity against tyrosinase from cotton bollworm. To get more information about the structure, we prepared a single crystal of the title compound and its crystal will be reported herein.

The bond distances between N2 and C7 is 1.277 (3) Å, which is in the range of typical bond length of imine double bond. The bond distance of 1.683 (2) Å for the thiocarbonyl group (S1–C8) is about the average value of the typical C=S double bond (1.56 Å) and C–S single bond (1.82 Å), showing a partial double bond character in feature. The partial double bond character also appears between N3 and C8 as well as N4 and C8, which show the distance of 1.355 (3) and 1.322 (3) Å, respectively. In the cryatal structure, there are three intermolecular hydrogen bonds: N3–H3···S1, N4–H4···N1, N4–H4···Cl1 (Table 1).

Experimental

1.6 g (10 mmol) 2-Chloro-5-methylnicotinaldehyde was dissolved in anhydrous ethanol (15 ml). To this solution, 0.91 g (10 mmol) thiosemicarbazide and 0.5 mL acetic acid were added. The mixture was refluxed for 24 h and then cooled to room temperatur. The precipitate was formed and collected after filteration. The title compound was obtained in 89% yield after recrystallization of the precipitate from anhydrous MeOH. The colourless crystals suitable for X-ray crystallography was carefully grown from anhydrous methanolic solution.

Refinement

All H atoms were placed in geometrically idealized positions(C—H = 0.93-0.96 Å, N—H=0.86 Å) and treated as riding on their parent atoms, with Uiso(H) = 1.2-1.5Ueq(C,N).

Figures

Fig. 1.
The molecular structure of the title compound , showing the labelling scheme. Displacement ellipsoids are drawn at the 30% probability level for all non-H atoms.
Fig. 2.
Packing diagram for the title compound viewed along the a axis.

Crystal data

C8H9ClN4SF(000) = 472
Mr = 228.70Dx = 1.488 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54186 Å
Hall symbol: -P 2ybcCell parameters from 658 reflections
a = 8.776 (3) Åθ = 3.1–66.2°
b = 15.523 (4) ŵ = 4.95 mm1
c = 7.540 (2) ÅT = 173 K
β = 96.193 (16)°Block, colorless
V = 1021.2 (5) Å30.45 × 0.30 × 0.30 mm
Z = 4

Data collection

Rigaku R-AXIS Rapid diffractometer1847 independent reflections
Radiation source: rotating anode1598 reflections with I > 2σ(I)
graphiteRint = 0.048
ω scans at fixed χ = 45°θmax = 68.3°, θmin = 5.1°
Absorption correction: numerical (ABSCOR; Higashi, 1995)h = −10→9
Tmin = 0.214, Tmax = 0.319k = −18→17
6565 measured reflectionsl = −8→9

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.105w = 1/[σ2(Fo2) + (0.0431P)2 + 0.4188P] where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.001
1847 reflectionsΔρmax = 0.27 e Å3
129 parametersΔρmin = −0.22 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0051 (7)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Cl10.50443 (6)0.31852 (4)0.16529 (8)0.0385 (2)
S11.21803 (7)0.48033 (4)−0.12061 (9)0.0413 (2)
N10.5116 (2)0.15225 (14)0.1900 (3)0.0341 (5)
N20.9510 (2)0.28984 (13)−0.0128 (2)0.0309 (5)
N31.0139 (2)0.36918 (13)−0.0313 (3)0.0349 (5)
H3B0.96870.41450.00970.042*
N41.2069 (2)0.31191 (13)−0.1757 (3)0.0380 (5)
H4A1.16450.2609−0.16690.046*
H4B1.29140.3171−0.22810.046*
C10.5935 (3)0.21864 (16)0.1461 (3)0.0308 (5)
C20.7391 (2)0.21399 (15)0.0899 (3)0.0289 (5)
C30.7996 (3)0.13151 (16)0.0783 (3)0.0315 (5)
H3A0.89790.12460.03850.038*
C40.7192 (3)0.05922 (17)0.1237 (3)0.0336 (5)
C50.5753 (3)0.07344 (16)0.1798 (3)0.0357 (6)
H5A0.51860.02490.21290.043*
C60.7836 (3)−0.03035 (16)0.1176 (3)0.0407 (6)
H6A0.8908−0.03020.16990.061*
H6B0.7779−0.0498−0.00670.061*
H6C0.7241−0.06940.18540.061*
C70.8228 (3)0.29122 (16)0.0529 (3)0.0340 (5)
H7A0.78040.34550.07870.041*
C81.1438 (3)0.38067 (15)−0.1105 (3)0.0305 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0293 (3)0.0389 (4)0.0493 (4)0.0043 (2)0.0141 (3)0.0027 (2)
S10.0337 (4)0.0357 (4)0.0589 (4)−0.0051 (3)0.0259 (3)−0.0051 (3)
N10.0275 (10)0.0380 (11)0.0387 (11)0.0010 (9)0.0119 (8)0.0023 (9)
N20.0255 (10)0.0368 (11)0.0313 (10)−0.0025 (8)0.0063 (8)0.0003 (8)
N30.0256 (10)0.0369 (12)0.0449 (12)−0.0032 (8)0.0155 (9)−0.0046 (9)
N40.0283 (11)0.0369 (12)0.0519 (13)−0.0026 (8)0.0184 (9)−0.0073 (9)
C10.0266 (12)0.0381 (14)0.0284 (11)0.0031 (10)0.0057 (9)−0.0013 (9)
C20.0242 (11)0.0374 (14)0.0263 (11)−0.0030 (9)0.0075 (9)−0.0010 (9)
C30.0230 (11)0.0434 (14)0.0293 (12)0.0010 (10)0.0080 (9)−0.0014 (10)
C40.0290 (12)0.0422 (14)0.0307 (12)0.0001 (10)0.0080 (9)−0.0007 (10)
C50.0311 (13)0.0357 (14)0.0422 (13)−0.0027 (10)0.0122 (10)0.0020 (10)
C60.0385 (14)0.0381 (15)0.0474 (15)0.0015 (11)0.0138 (12)0.0007 (11)
C70.0283 (12)0.0341 (13)0.0413 (14)−0.0017 (10)0.0115 (10)−0.0002 (10)
C80.0230 (11)0.0371 (14)0.0325 (12)−0.0019 (9)0.0078 (9)−0.0004 (9)

Geometric parameters (Å, °)

Cl1—C11.749 (2)C2—C31.392 (3)
S1—C81.683 (2)C2—C71.449 (3)
N1—C11.319 (3)C3—C41.388 (3)
N1—C51.350 (3)C3—H3A0.9500
N2—C71.277 (3)C4—C51.393 (3)
N2—N31.363 (3)C4—C61.503 (3)
N3—C81.355 (3)C5—H5A0.9500
N3—H3B0.8800C6—H6A0.9800
N4—C81.322 (3)C6—H6B0.9800
N4—H4A0.8800C6—H6C0.9800
N4—H4B0.8800C7—H7A0.9500
C1—C21.391 (3)
C1—N1—C5117.0 (2)C3—C4—C6122.5 (2)
C7—N2—N3114.1 (2)C5—C4—C6120.8 (2)
C8—N3—N2122.2 (2)N1—C5—C4123.7 (2)
C8—N3—H3B118.9N1—C5—H5A118.1
N2—N3—H3B118.9C4—C5—H5A118.1
C8—N4—H4A120.0C4—C6—H6A109.5
C8—N4—H4B120.0C4—C6—H6B109.5
H4A—N4—H4B120.0H6A—C6—H6B109.5
N1—C1—C2125.4 (2)C4—C6—H6C109.5
N1—C1—Cl1114.30 (17)H6A—C6—H6C109.5
C2—C1—Cl1120.30 (19)H6B—C6—H6C109.5
C1—C2—C3115.8 (2)N2—C7—C2123.2 (2)
C1—C2—C7121.2 (2)N2—C7—H7A118.4
C3—C2—C7123.0 (2)C2—C7—H7A118.4
C4—C3—C2121.4 (2)N4—C8—N3117.7 (2)
C4—C3—H3A119.3N4—C8—S1123.06 (18)
C2—C3—H3A119.3N3—C8—S1119.29 (18)
C3—C4—C5116.7 (2)
C7—N2—N3—C8−175.1 (2)C2—C3—C4—C6−178.2 (2)
C5—N1—C1—C20.2 (3)C1—N1—C5—C4−1.0 (3)
C5—N1—C1—Cl1−179.23 (17)C3—C4—C5—N10.7 (4)
N1—C1—C2—C30.8 (3)C6—C4—C5—N1179.4 (2)
Cl1—C1—C2—C3−179.73 (16)N3—N2—C7—C2−177.63 (19)
N1—C1—C2—C7−177.0 (2)C1—C2—C7—N2−174.1 (2)
Cl1—C1—C2—C72.5 (3)C3—C2—C7—N28.3 (4)
C1—C2—C3—C4−1.2 (3)N2—N3—C8—N42.0 (3)
C7—C2—C3—C4176.6 (2)N2—N3—C8—S1−177.57 (16)
C2—C3—C4—C50.5 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3B···S1i0.882.523.379 (2)166
N4—H4B···N1ii0.882.153.012 (3)168
N4—H4B···Cl1ii0.882.983.609 (2)130

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DS2018).

References

  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Kramer, K. J. & Knost, M. R. (2001). Tetrahedron, 57, 385-392.
  • Liu, J., Yi, W., Wan, Y., Ma, L. & Song, H. (2008). Bioorg. Med. Chem.16, 1096–1102. [PubMed]
  • Rigaku (2001). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Xue, C.-B., Zhang, L., Luo, W.-C., Xie, X.-Y., Jiang, L. & Xiao, T. (2007). Bioorg. Med. Chem.15, 2006–2015. [PubMed]

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