(E)-1-[(2-Chloro-5-methyl-pyridin-3-yl)methyl-ene]thiosemicarbazide.

The title compound, C(8)H(9)ClN(4)S, which has potential insecticidal activity, was synthesized by the reaction of 2-chloro-5-methyl-nicotinaldehyde and thio-semicarbazide. In the crystal structure, the mol-ecules are linked via inter-molecular 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 ▶). For the inhibitory activity on tyrosinase of benzaldehyde thio­semi­carbazones, see: Xue et al. (2007 ▶). For the synthesis of the title compound, see: Liu et al. (2008 ▶).

Experimental

Crystal data

C8H9ClN4S

M = 228.70

Monoclinic,

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

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

C8H9ClN4S	F(000) = 472
Mr = 228.70	Dx = 1.488 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54186 Å
Hall symbol: -P 2ybc	Cell parameters from 658 reflections
a = 8.776 (3) Å	θ = 3.1–66.2°
b = 15.523 (4) Å	µ = 4.95 mm−1
c = 7.540 (2) Å	T = 173 K
β = 96.193 (16)°	Block, colorless
V = 1021.2 (5) Å3	0.45 × 0.30 × 0.30 mm
Z = 4

Rigaku R-AXIS Rapid diffractometer	1847 independent reflections
Radiation source: rotating anode	1598 reflections with I > 2σ(I)
graphite	Rint = 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 = 0.319	k = −18→17
6565 measured reflections	l = −8→9

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

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.

	x	y	z	Uiso*/Ueq
Cl1	0.50443 (6)	0.31852 (4)	0.16529 (8)	0.0385 (2)
S1	1.21803 (7)	0.48033 (4)	−0.12061 (9)	0.0413 (2)
N1	0.5116 (2)	0.15225 (14)	0.1900 (3)	0.0341 (5)
N2	0.9510 (2)	0.28984 (13)	−0.0128 (2)	0.0309 (5)
N3	1.0139 (2)	0.36918 (13)	−0.0313 (3)	0.0349 (5)
H3B	0.9687	0.4145	0.0097	0.042*
N4	1.2069 (2)	0.31191 (13)	−0.1757 (3)	0.0380 (5)
H4A	1.1645	0.2609	−0.1669	0.046*
H4B	1.2914	0.3171	−0.2281	0.046*
C1	0.5935 (3)	0.21864 (16)	0.1461 (3)	0.0308 (5)
C2	0.7391 (2)	0.21399 (15)	0.0899 (3)	0.0289 (5)
C3	0.7996 (3)	0.13151 (16)	0.0783 (3)	0.0315 (5)
H3A	0.8979	0.1246	0.0385	0.038*
C4	0.7192 (3)	0.05922 (17)	0.1237 (3)	0.0336 (5)
C5	0.5753 (3)	0.07344 (16)	0.1798 (3)	0.0357 (6)
H5A	0.5186	0.0249	0.2129	0.043*
C6	0.7836 (3)	−0.03035 (16)	0.1176 (3)	0.0407 (6)
H6A	0.8908	−0.0302	0.1699	0.061*
H6B	0.7779	−0.0498	−0.0067	0.061*
H6C	0.7241	−0.0694	0.1854	0.061*
C7	0.8228 (3)	0.29122 (16)	0.0529 (3)	0.0340 (5)
H7A	0.7804	0.3455	0.0787	0.041*
C8	1.1438 (3)	0.38067 (15)	−0.1105 (3)	0.0305 (5)

	U11	U22	U33	U12	U13	U23
Cl1	0.0293 (3)	0.0389 (4)	0.0493 (4)	0.0043 (2)	0.0141 (3)	0.0027 (2)
S1	0.0337 (4)	0.0357 (4)	0.0589 (4)	−0.0051 (3)	0.0259 (3)	−0.0051 (3)
N1	0.0275 (10)	0.0380 (11)	0.0387 (11)	0.0010 (9)	0.0119 (8)	0.0023 (9)
N2	0.0255 (10)	0.0368 (11)	0.0313 (10)	−0.0025 (8)	0.0063 (8)	0.0003 (8)
N3	0.0256 (10)	0.0369 (12)	0.0449 (12)	−0.0032 (8)	0.0155 (9)	−0.0046 (9)
N4	0.0283 (11)	0.0369 (12)	0.0519 (13)	−0.0026 (8)	0.0184 (9)	−0.0073 (9)
C1	0.0266 (12)	0.0381 (14)	0.0284 (11)	0.0031 (10)	0.0057 (9)	−0.0013 (9)
C2	0.0242 (11)	0.0374 (14)	0.0263 (11)	−0.0030 (9)	0.0075 (9)	−0.0010 (9)
C3	0.0230 (11)	0.0434 (14)	0.0293 (12)	0.0010 (10)	0.0080 (9)	−0.0014 (10)
C4	0.0290 (12)	0.0422 (14)	0.0307 (12)	0.0001 (10)	0.0080 (9)	−0.0007 (10)
C5	0.0311 (13)	0.0357 (14)	0.0422 (13)	−0.0027 (10)	0.0122 (10)	0.0020 (10)
C6	0.0385 (14)	0.0381 (15)	0.0474 (15)	0.0015 (11)	0.0138 (12)	0.0007 (11)
C7	0.0283 (12)	0.0341 (13)	0.0413 (14)	−0.0017 (10)	0.0115 (10)	−0.0002 (10)
C8	0.0230 (11)	0.0371 (14)	0.0325 (12)	−0.0019 (9)	0.0078 (9)	−0.0004 (9)

Cl1—C1	1.749 (2)	C2—C3	1.392 (3)
S1—C8	1.683 (2)	C2—C7	1.449 (3)
N1—C1	1.319 (3)	C3—C4	1.388 (3)
N1—C5	1.350 (3)	C3—H3A	0.9500
N2—C7	1.277 (3)	C4—C5	1.393 (3)
N2—N3	1.363 (3)	C4—C6	1.503 (3)
N3—C8	1.355 (3)	C5—H5A	0.9500
N3—H3B	0.8800	C6—H6A	0.9800
N4—C8	1.322 (3)	C6—H6B	0.9800
N4—H4A	0.8800	C6—H6C	0.9800
N4—H4B	0.8800	C7—H7A	0.9500
C1—C2	1.391 (3)
C1—N1—C5	117.0 (2)	C3—C4—C6	122.5 (2)
C7—N2—N3	114.1 (2)	C5—C4—C6	120.8 (2)
C8—N3—N2	122.2 (2)	N1—C5—C4	123.7 (2)
C8—N3—H3B	118.9	N1—C5—H5A	118.1
N2—N3—H3B	118.9	C4—C5—H5A	118.1
C8—N4—H4A	120.0	C4—C6—H6A	109.5
C8—N4—H4B	120.0	C4—C6—H6B	109.5
H4A—N4—H4B	120.0	H6A—C6—H6B	109.5
N1—C1—C2	125.4 (2)	C4—C6—H6C	109.5
N1—C1—Cl1	114.30 (17)	H6A—C6—H6C	109.5
C2—C1—Cl1	120.30 (19)	H6B—C6—H6C	109.5
C1—C2—C3	115.8 (2)	N2—C7—C2	123.2 (2)
C1—C2—C7	121.2 (2)	N2—C7—H7A	118.4
C3—C2—C7	123.0 (2)	C2—C7—H7A	118.4
C4—C3—C2	121.4 (2)	N4—C8—N3	117.7 (2)
C4—C3—H3A	119.3	N4—C8—S1	123.06 (18)
C2—C3—H3A	119.3	N3—C8—S1	119.29 (18)
C3—C4—C5	116.7 (2)
C7—N2—N3—C8	−175.1 (2)	C2—C3—C4—C6	−178.2 (2)
C5—N1—C1—C2	0.2 (3)	C1—N1—C5—C4	−1.0 (3)
C5—N1—C1—Cl1	−179.23 (17)	C3—C4—C5—N1	0.7 (4)
N1—C1—C2—C3	0.8 (3)	C6—C4—C5—N1	179.4 (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—C7	2.5 (3)	C3—C2—C7—N2	8.3 (4)
C1—C2—C3—C4	−1.2 (3)	N2—N3—C8—N4	2.0 (3)
C7—C2—C3—C4	176.6 (2)	N2—N3—C8—S1	−177.57 (16)
C2—C3—C4—C5	0.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···S1i	0.88	2.52	3.379 (2)	166
N4—H4B···N1ii	0.88	2.15	3.012 (3)	168
N4—H4B···Cl1ii	0.88	2.98	3.609 (2)	130

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯S1i	0.88	2.52	3.379 (2)	166
N4—H4B⋯N1ii	0.88	2.15	3.012 (3)	168
N4—H4B⋯Cl1ii	0.88	2.98	3.609 (2)	130

Symmetry codes: (i) ; (ii) .