4-Methyl-1-(3-pyridyl­methyl­idene)thio­semicarbazide

Li, R.

doi:10.1107/S1600536810048853

organic compounds

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Volume 66| Part 12| December 2010| Page o3324

https://doi.org/10.1107/S1600536810048853

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4-Methyl-1-(3-pyridylmethylidene)thiosemicarbazide

Rongchun Li ^a ^*

^aDepartment of Chemistry, Dezhou University, Dezhou 253023, People's Republic of China
^*Correspondence e-mail: rongchunli01@126.com

(Received 22 November 2010; accepted 23 November 2010; online 27 November 2010)

All the non-H atoms of the title compound, C₈H₁₀N₄S, lie on a crystallographic mirror plane and an intramolecular N—H⋯N hydrogen bond helps to stabilize the molecular conformation. In the crystal, molecules are linked through intermolecular N—H⋯N hydrogen bonds, forming zigzag C(7) chains along the a axis.

Related literature

For background to Schiff bases derived from thiosemicarbazone and its derivatives, see: Casas et al. (2001 ); Beraldo et al. (2001 ); Jouad et al. (2002 ); Swearingen et al. (2002 ). For bond-length data, see: Allen et al. (1987 ). For similar structures, see: Selvanayagam et al. (2002 ); Karakurt et al. (2003 ); Bernhardt et al. (2003 ); Sampath et al. (2003 ).

Experimental

Crystal data

C₈H₁₀N₄S
M_r = 194.26
Monoclinic, P 2₁ /m
a = 7.276 (3) Å
b = 6.581 (2) Å
c = 10.297 (3) Å
β = 92.997 (2)°
V = 492.4 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 298 K
0.17 × 0.15 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.953, T_max = 0.958
3208 measured reflections
1106 independent reflections
640 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.118
S = 1.02
1106 reflections
84 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯N2	0.90 (2)	2.14 (3)	2.585 (4)	109 (2)
N3—H3⋯N1ⁱ	0.90 (1)	2.09 (1)	2.989 (3)	176 (3)
Symmetry code: (i) x+1, y, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810048853/hb5755sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810048853/hb5755Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazone and its derivatives are important materials for the preparation of Schiff bases (Casas et al., 2001; Beraldo et al., 2001; Jouad et al., 2002; Swearingen et al., 2002). In this paper, the title new Schiff base compound derived from the condensation of 3-formylpyridine with 4-methylthiosemicarbazone is reported.

The molecule of the title compound, Fig. 1, possess a crystallographic mirror plane symmetry. The bond lengths have normal values (Allen et al., 1987), and are comparable to those observed in similar compounds (Selvanayagam et al., 2002; Karakurt et al., 2003; Bernhardt et al., 2003; Sampath et al., 2003).

In the crystal, molecules are linked through intermolecular N—H···N hydrogen bonds (Table 1), to form zigzag chains along the a axis (Fig. 2).

Related literature top

For background to Schiff bases derived from thiosemicarbazone and its derivatives, see: Casas et al. (2001); Beraldo et al. (2001); Jouad et al. (2002); Swearingen et al. (2002). For bond-length data, see: Allen et al. (1987). For similar structures, see: Selvanayagam et al. (2002); Karakurt et al. (2003); Bernhardt et al. (2003); Sampath et al. (2003).

Experimental top

The title compound was prepared by the Schiff base condensation of equimolar quantities of 3-formylpyridine (0.107 g, 1 mmol) with 4-methylthiosemicarbazone (0.105 g, 1 mmol) in methanol. The excess methanol was removed by distillation. Colourless blocks were obtained by slow evaporation of an ethanol solution of the product in air.

Structure description top

In the crystal, molecules are linked through intermolecular N—H···N hydrogen bonds (Table 1), to form zigzag chains along the a axis (Fig. 2).

For background to Schiff bases derived from thiosemicarbazone and its derivatives, see: Casas et al. (2001); Beraldo et al. (2001); Jouad et al. (2002); Swearingen et al. (2002). For bond-length data, see: Allen et al. (1987). For similar structures, see: Selvanayagam et al. (2002); Karakurt et al. (2003); Bernhardt et al. (2003); Sampath et al. (2003).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. The crystal packing of the title compound, viewed along the b axis.

4-Methyl-1-(3-pyridylmethylidene)thiosemicarbazide top

Crystal data top

C₈H₁₀N₄S	F(000) = 204
M_r = 194.26	D_x = 1.310 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 669 reflections
a = 7.276 (3) Å	θ = 2.7–24.5°
b = 6.581 (2) Å	µ = 0.29 mm⁻¹
c = 10.297 (3) Å	T = 298 K
β = 92.997 (2)°	Block, colourless
V = 492.4 (3) Å³	0.17 × 0.15 × 0.15 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1106 independent reflections
Radiation source: fine-focus sealed tube	640 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ω scans	θ_max = 26.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −9→9
T_min = 0.953, T_max = 0.958	k = −8→8
3208 measured reflections	l = −12→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0547P)²] where P = (F_o² + 2F_c²)/3
1106 reflections	(Δ/σ)_max < 0.001
84 parameters	Δρ_max = 0.14 e Å⁻³
2 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₈H₁₀N₄S	V = 492.4 (3) Å³
M_r = 194.26	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 7.276 (3) Å	µ = 0.29 mm⁻¹
b = 6.581 (2) Å	T = 298 K
c = 10.297 (3) Å	0.17 × 0.15 × 0.15 mm
β = 92.997 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1106 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	640 reflections with I > 2σ(I)
T_min = 0.953, T_max = 0.958	R_int = 0.041
3208 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	2 restraints
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.14 e Å⁻³
1106 reflections	Δρ_min = −0.20 e Å⁻³
84 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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.68926 (12)	0.2500	0.29184 (9)	0.0835 (4)
N1	−0.2929 (3)	0.2500	−0.1051 (2)	0.0558 (7)
N2	0.2508 (3)	0.2500	0.0542 (2)	0.0507 (6)
N3	0.4324 (3)	0.2500	0.1009 (2)	0.0566 (7)
N4	0.3217 (4)	0.2500	0.3028 (3)	0.0699 (8)
C1	0.0350 (3)	0.2500	−0.1287 (3)	0.0496 (7)
C2	−0.1201 (3)	0.2500	−0.0547 (3)	0.0510 (8)
H2	−0.1020	0.2500	0.0354	0.061*
C3	−0.3159 (4)	0.2500	−0.2351 (3)	0.0616 (9)
H3A	−0.4353	0.2500	−0.2720	0.074*
C4	−0.1733 (4)	0.2500	−0.3164 (3)	0.0697 (10)
H4A	−0.1954	0.2500	−0.4061	0.084*
C5	0.0049 (4)	0.2500	−0.2620 (3)	0.0673 (10)
H5	0.1041	0.2500	−0.3154	0.081*
C6	0.2213 (4)	0.2500	−0.0687 (3)	0.0581 (8)
H6	0.3209	0.2500	−0.1217	0.070*
C7	0.4698 (4)	0.2500	0.2318 (3)	0.0554 (8)
C8	0.3272 (5)	0.2500	0.4451 (3)	0.0994 (13)
H8A	0.3310	0.1125	0.4762	0.149*	0.50
H8B	0.2193	0.3162	0.4743	0.149*	0.50
H8C	0.4349	0.3213	0.4781	0.149*	0.50
H3	0.519 (3)	0.2500	0.042 (2)	0.080*
H4	0.212 (2)	0.2500	0.259 (3)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0681 (6)	0.1189 (9)	0.0617 (6)	0.000	−0.0150 (4)	0.000
N1	0.0392 (13)	0.0640 (17)	0.0642 (17)	0.000	0.0028 (12)	0.000
N2	0.0365 (12)	0.0615 (16)	0.0542 (15)	0.000	0.0019 (11)	0.000
N3	0.0416 (13)	0.0775 (18)	0.0508 (16)	0.000	0.0024 (11)	0.000
N4	0.0738 (18)	0.085 (2)	0.0518 (16)	0.000	0.0136 (14)	0.000
C1	0.0369 (14)	0.0618 (19)	0.0503 (17)	0.000	0.0058 (12)	0.000
C2	0.0425 (15)	0.0593 (19)	0.0512 (18)	0.000	0.0011 (13)	0.000
C3	0.0450 (16)	0.074 (2)	0.064 (2)	0.000	−0.0062 (15)	0.000
C4	0.0587 (19)	0.102 (3)	0.0478 (19)	0.000	−0.0054 (16)	0.000
C5	0.0505 (18)	0.097 (3)	0.055 (2)	0.000	0.0091 (15)	0.000
C6	0.0389 (15)	0.078 (2)	0.0579 (19)	0.000	0.0108 (13)	0.000
C7	0.0624 (19)	0.0541 (19)	0.0499 (18)	0.000	0.0033 (15)	0.000
C8	0.126 (3)	0.121 (4)	0.053 (2)	0.000	0.023 (2)	0.000

Geometric parameters (Å, º) top

S1—C7	1.682 (3)	C1—C6	1.460 (4)
N1—C2	1.335 (3)	C2—H2	0.9300
N1—C3	1.340 (3)	C3—C4	1.367 (4)
N2—C6	1.273 (4)	C3—H3A	0.9300
N2—N3	1.382 (3)	C4—C5	1.385 (4)
N3—C7	1.361 (4)	C4—H4A	0.9300
N3—H3	0.899 (10)	C5—H5	0.9300
N4—C7	1.334 (4)	C6—H6	0.9300
N4—C8	1.463 (4)	C8—H8A	0.9600
N4—H4	0.898 (10)	C8—H8B	0.9600
C1—C5	1.379 (4)	C8—H8C	0.9600
C1—C2	1.394 (4)

C2—N1—C3	117.0 (2)	C3—C4—H4A	120.8
C6—N2—N3	117.1 (2)	C5—C4—H4A	120.8
C7—N3—N2	118.9 (2)	C1—C5—C4	119.9 (3)
C7—N3—H3	124 (2)	C1—C5—H5	120.0
N2—N3—H3	117 (2)	C4—C5—H5	120.0
C7—N4—C8	124.7 (3)	N2—C6—C1	121.7 (3)
C7—N4—H4	117 (2)	N2—C6—H6	119.2
C8—N4—H4	119 (2)	C1—C6—H6	119.2
C5—C1—C2	117.0 (2)	N4—C7—N3	114.7 (3)
C5—C1—C6	121.1 (3)	N4—C7—S1	125.2 (2)
C2—C1—C6	121.9 (3)	N3—C7—S1	120.1 (2)
N1—C2—C1	124.1 (2)	N4—C8—H8A	109.5
N1—C2—H2	118.0	N4—C8—H8B	109.5
C1—C2—H2	118.0	H8A—C8—H8B	109.5
N1—C3—C4	123.6 (3)	N4—C8—H8C	109.5
N1—C3—H3A	118.2	H8A—C8—H8C	109.5
C4—C3—H3A	118.2	H8B—C8—H8C	109.5
C3—C4—C5	118.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N2	0.90 (2)	2.14 (3)	2.585 (4)	109 (2)
N3—H3···N1ⁱ	0.90 (1)	2.09 (1)	2.989 (3)	176 (3)

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

Experimental details

Crystal data
Chemical formula	C₈H₁₀N₄S
M_r	194.26
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	298
a, b, c (Å)	7.276 (3), 6.581 (2), 10.297 (3)
β (°)	92.997 (2)
V (Å³)	492.4 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.17 × 0.15 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.953, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	3208, 1106, 640
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.118, 1.02
No. of reflections	1106
No. of parameters	84
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.20

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N2	0.90 (2)	2.14 (3)	2.585 (4)	109 (2)
N3—H3···N1ⁱ	0.899 (10)	2.091 (11)	2.989 (3)	176 (3)

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

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3324

https://doi.org/10.1107/S1600536810048853

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