4-Methyl-1-[4-(methyl­sulfan­yl)benzyl­idene]thio­semicarbazide

Mu, X.-G.; Wang, X.-J.; Yang, J.-J.

doi:10.1107/S1600536811028029

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2069

doi:10.1107/S1600536811028029

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4-Methyl-1-[4-(methylsulfanyl)benzylidene]thiosemicarbazide

Xiao-Gang Mu,^a ^* Xuan-Jun Wang ^a and Jing-Jing Yang ^a

^aNo. 503 Faculty, Xi'an Research Institute of High Technology, Hongqing Town., Xi'an 710025, People's Republic of China
^*Correspondence e-mail: zhouliyou111@163.com

(Received 31 May 2011; accepted 13 July 2011; online 16 July 2011)

The title compound, C₁₀H₁₃N₃S₂, is roughly planar (r.m.s. deviation = 0.086 Å). In the crystal, N—H⋯S hydrogen bonds link the molecules into (001) sheets.

Related literature

For a related structure, see: Li & Jian (2010 ).

Experimental

Crystal data

C₁₀H₁₃N₃S₂
M_r = 239.35
Monoclinic, C 2/c
a = 14.123 (3) Å
b = 7.7789 (16) Å
c = 21.384 (4) Å
β = 96.31 (3)°
V = 2335.1 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 293 K
0.23 × 0.18 × 0.17 mm

Data collection

Bruker SMART CCD diffractometer
10756 measured reflections
2680 independent reflections
2368 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.170
S = 1.35
2680 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯S2ⁱ	0.86	2.48	3.3195 (17)	166
N1—H1A⋯S2ⁱⁱ	0.86	2.72	3.430 (2)	141
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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: 10.1107/S1600536811028029/hb5903sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028029/hb5903Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811028029/hb5903Isup3.cml

checkCIF report

Related literature top

For a related structure, see: Li & Jian (2010).

Experimental top

A mixture of 4-methylthiosemicarbazide (0.1 mol), and 4-(methylthio)benzaldehyde (0.1 mol) was stirred in refluxing ethanol (20 mL) for 4 h to afford the title compound (0.076 mol, yield 76%). Colourless blocks of the title compound were obtained by recrystallization from ethanol at room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 structure of the title compound showing 50% probability displacement ellipsoids.

4-Methyl-1-[4-(methylsulfanyl)benzylidene]thiosemicarbazide top

Crystal data top

C₁₀H₁₃N₃S₂	F(000) = 1008
M_r = 239.35	D_x = 1.362 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.123 (3) Å	Cell parameters from 2368 reflections
b = 7.7789 (16) Å	θ = 2.9–27.5°
c = 21.384 (4) Å	µ = 0.43 mm⁻¹
β = 96.31 (3)°	T = 293 K
V = 2335.1 (8) Å³	Bar, colorless
Z = 8	0.23 × 0.18 × 0.17 mm

Data collection top

Bruker SMART CCD diffractometer	2368 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.043
Graphite monochromator	θ_max = 27.5°, θ_min = 3.0°
phi and ω scans	h = −18→18
10756 measured reflections	k = −10→10
2680 independent reflections	l = −27→27

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.170	H-atom parameters constrained
S = 1.35	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
2680 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.71 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₀H₁₃N₃S₂	V = 2335.1 (8) Å³
M_r = 239.35	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 14.123 (3) Å	µ = 0.43 mm⁻¹
b = 7.7789 (16) Å	T = 293 K
c = 21.384 (4) Å	0.23 × 0.18 × 0.17 mm
β = 96.31 (3)°

Data collection top

Bruker SMART CCD diffractometer	2368 reflections with I > 2σ(I)
10756 measured reflections	R_int = 0.043
2680 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.170	H-atom parameters constrained
S = 1.35	Δρ_max = 0.71 e Å⁻³
2680 reflections	Δρ_min = −0.34 e Å⁻³
136 parameters

Special details top

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 > 2sigma(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
S2	0.62610 (3)	0.59132 (7)	0.31409 (2)	0.0160 (2)
S1	0.65713 (4)	−0.10944 (9)	−0.11046 (3)	0.0285 (2)
N3	0.59872 (11)	0.4593 (3)	0.19951 (7)	0.0165 (4)
H3A	0.5447	0.5113	0.1957	0.020*
N2	0.62552 (12)	0.3592 (2)	0.15110 (7)	0.0170 (4)
N1	0.74248 (12)	0.3948 (3)	0.25443 (8)	0.0180 (4)
H1A	0.7538	0.3359	0.2221	0.022*
C9	0.65908 (13)	0.4741 (3)	0.25306 (9)	0.0152 (4)
C2	0.62751 (14)	0.0364 (3)	−0.05305 (9)	0.0189 (4)
C5	0.59070 (13)	0.2501 (3)	0.04735 (8)	0.0156 (4)
C7	0.69010 (14)	0.0413 (3)	0.00246 (9)	0.0203 (5)
H7A	0.7441	−0.0280	0.0063	0.024*
C3	0.54653 (14)	0.1405 (3)	−0.05812 (9)	0.0191 (4)
H3B	0.5048	0.1399	−0.0949	0.023*
C6	0.67274 (13)	0.1475 (3)	0.05149 (9)	0.0181 (4)
H6A	0.7158	0.1510	0.0876	0.022*
C8	0.56888 (13)	0.3578 (3)	0.09981 (9)	0.0166 (4)
H8A	0.5142	0.4253	0.0961	0.020*
C10	0.81565 (14)	0.4023 (3)	0.30768 (9)	0.0197 (5)
H10A	0.8697	0.3356	0.2986	0.030*
H10B	0.7909	0.3565	0.3443	0.030*
H10C	0.8347	0.5195	0.3153	0.030*
C4	0.52844 (13)	0.2450 (3)	−0.00809 (9)	0.0185 (4)
H4A	0.4739	0.3127	−0.0116	0.022*
C1	0.56946 (16)	−0.0720 (3)	−0.17628 (10)	0.0233 (5)
H1B	0.5809	−0.1476	−0.2101	0.035*
H1C	0.5735	0.0452	−0.1899	0.035*
H1D	0.5071	−0.0934	−0.1641	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S2	0.0166 (3)	0.0151 (3)	0.0165 (3)	−0.00181 (16)	0.0024 (2)	−0.00314 (17)
S1	0.0262 (4)	0.0342 (4)	0.0247 (3)	0.0075 (2)	0.0007 (2)	−0.0115 (2)
N3	0.0154 (8)	0.0176 (10)	0.0163 (8)	0.0021 (6)	0.0008 (6)	−0.0041 (7)
N2	0.0205 (8)	0.0147 (10)	0.0163 (8)	−0.0016 (7)	0.0041 (6)	−0.0018 (7)
N1	0.0169 (8)	0.0198 (11)	0.0170 (8)	0.0007 (6)	0.0009 (6)	−0.0052 (6)
C9	0.0168 (9)	0.0116 (11)	0.0172 (9)	−0.0041 (7)	0.0026 (6)	0.0002 (7)
C2	0.0205 (10)	0.0183 (12)	0.0184 (9)	−0.0014 (8)	0.0046 (7)	−0.0013 (8)
C5	0.0206 (9)	0.0118 (11)	0.0147 (8)	−0.0031 (7)	0.0035 (6)	0.0016 (7)
C7	0.0170 (9)	0.0220 (13)	0.0220 (10)	0.0012 (8)	0.0031 (7)	−0.0003 (8)
C3	0.0208 (10)	0.0200 (13)	0.0161 (9)	−0.0015 (8)	−0.0003 (7)	0.0002 (8)
C6	0.0187 (10)	0.0185 (12)	0.0168 (9)	−0.0018 (8)	0.0008 (7)	0.0009 (8)
C8	0.0179 (9)	0.0145 (12)	0.0175 (9)	−0.0015 (7)	0.0021 (7)	0.0006 (8)
C10	0.0157 (10)	0.0222 (13)	0.0207 (10)	−0.0005 (7)	−0.0008 (7)	−0.0020 (8)
C4	0.0198 (10)	0.0165 (12)	0.0190 (9)	0.0011 (7)	0.0009 (7)	0.0026 (8)
C1	0.0310 (11)	0.0201 (13)	0.0194 (10)	−0.0045 (8)	0.0049 (8)	−0.0019 (8)

Geometric parameters (Å, º) top

S2—C9	1.699 (2)	C5—C8	1.460 (3)
S1—C2	1.756 (2)	C7—C6	1.378 (3)
S1—C1	1.793 (2)	C7—H7A	0.9300
N3—C9	1.355 (2)	C3—C4	1.389 (3)
N3—N2	1.381 (2)	C3—H3B	0.9300
N3—H3A	0.8600	C6—H6A	0.9300
N2—C8	1.285 (2)	C8—H8A	0.9300
N1—C9	1.327 (3)	C10—H10A	0.9600
N1—C10	1.452 (3)	C10—H10B	0.9600
N1—H1A	0.8600	C10—H10C	0.9600
C2—C3	1.396 (3)	C4—H4A	0.9300
C2—C7	1.401 (3)	C1—H1B	0.9600
C5—C4	1.397 (3)	C1—H1C	0.9600
C5—C6	1.402 (3)	C1—H1D	0.9600

C2—S1—C1	104.29 (10)	C2—C3—H3B	120.1
C9—N3—N2	118.85 (16)	C7—C6—C5	120.56 (17)
C9—N3—H3A	120.6	C7—C6—H6A	119.7
N2—N3—H3A	120.6	C5—C6—H6A	119.7
C8—N2—N3	116.64 (17)	N2—C8—C5	119.77 (18)
C9—N1—C10	123.52 (17)	N2—C8—H8A	120.1
C9—N1—H1A	118.2	C5—C8—H8A	120.1
C10—N1—H1A	118.2	N1—C10—H10A	109.5
N1—C9—N3	116.98 (18)	N1—C10—H10B	109.5
N1—C9—S2	123.37 (15)	H10A—C10—H10B	109.5
N3—C9—S2	119.65 (15)	N1—C10—H10C	109.5
C3—C2—C7	119.05 (19)	H10A—C10—H10C	109.5
C3—C2—S1	125.22 (15)	H10B—C10—H10C	109.5
C7—C2—S1	115.70 (16)	C3—C4—C5	121.24 (18)
C4—C5—C6	118.41 (17)	C3—C4—H4A	119.4
C4—C5—C8	120.17 (17)	C5—C4—H4A	119.4
C6—C5—C8	121.41 (17)	S1—C1—H1B	109.5
C6—C7—C2	120.85 (19)	S1—C1—H1C	109.5
C6—C7—H7A	119.6	H1B—C1—H1C	109.5
C2—C7—H7A	119.6	S1—C1—H1D	109.5
C4—C3—C2	119.87 (18)	H1B—C1—H1D	109.5
C4—C3—H3B	120.1	H1C—C1—H1D	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···S2ⁱ	0.86	2.48	3.3195 (17)	166
N1—H1A···S2ⁱⁱ	0.86	2.72	3.430 (2)	141

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₃S₂
M_r	239.35
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	14.123 (3), 7.7789 (16), 21.384 (4)
β (°)	96.31 (3)
V (Å³)	2335.1 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.23 × 0.18 × 0.17

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10756, 2680, 2368
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.170, 1.35
No. of reflections	2680
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.34

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), 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
N3—H3A···S2ⁱ	0.86	2.48	3.3195 (17)	166
N1—H1A···S2ⁱⁱ	0.86	2.72	3.430 (2)	141

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2.

Acknowledgements

The authors thank Yu-Feng Li (Weifang University) for the data collection and initial processing of the CIF.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Li, Y.-F. & Jian, F.-F. (2010). Acta Cryst. E66, o1720. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar