N-Methyl-2-(1-methyl-3-phenyl­prop-2-en-1-yl­idene)hydrazinecarbo­thio­amide

Fillipe Vieira Rocha; Adelino Vieira de Godoy Netto; Johannes Beck; Jörg Daniels; Adriano Bof de Oliveira

doi:10.1107/S1600536814013889

. 2014 Jun 21;70(Pt 7):o800. doi: 10.1107/S1600536814013889

N-Methyl-2-(1-methyl-3-phenylprop-2-en-1-ylidene)hydrazinecarbothioamide

Fillipe Vieira Rocha ^a, Adelino Vieira de Godoy Netto ^a, Johannes Beck ^b, Jörg Daniels ^b, Adriano Bof de Oliveira ^c,^*

PMCID: PMC4120594 PMID: 25161581

Abstract

In the title compound, C₁₂H₁₅N₃S, the molecule deviates slightly from planarity, with a maximum deviation from the mean plane of the non-H atoms of 0.2756 (6) Å for the S atom and a torsion angle for the N—N—C—N fragment of −7.04 (16)°. In the crystal, molecules are linked by N—H⋯S hydrogen-bond interactions, forming centrosymmetric dimers. Additionally, one weak intramolecular N—H⋯N hydrogen-bond interaction is observed. The crystal packing shows a herringbone arrangement viewed along the c axis.

Keywords: crystal structure

Related literature

For one of the first reports of the synthesis of thiosemicarbazone derivatives, see: Freund & Schander (1902 ▶). For a report of the antifungal activity of the title compound, see: Nishimura et al. (1979 ▶). graphic file with name e-70-0o800-scheme1.jpg

Experimental

Crystal data

C₁₂H₁₅N₃S
M _r = 233.33
Orthorhombic,
a = 10.5832 (2) Å
b = 7.9509 (2) Å
c = 28.9259 (5) Å
V = 2434.00 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 123 K
0.44 × 0.31 × 0.27 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (Blessing, 1995 ▶) T _min = 0.904, T _max = 0.955
26770 measured reflections
2783 independent reflections
2414 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.080
S = 1.05
2783 reflections
205 parameters
All H-atom parameters refined
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S1600536814013889/bx2460sup1.cif

e-70-0o800-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814013889/bx2460Isup2.hkl

e-70-0o800-Isup2.hkl^{(136.8KB, hkl)}

Click here for additional data file.^{(4.6KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814013889/bx2460Isup3.cml

CCDC reference: 1008277

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—HN3⋯N1	0.879 (17)	2.143 (16)	2.5877 (15)	110.7 (13)
N2—HN2⋯S1ⁱ	0.862 (18)	2.663 (18)	3.4296 (12)	148.7 (15)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We gratefully acknowledge financial support by the German Research Foundation (DFG) through the Collaborative Research Center SFB 813, Chemistry at Spin Centers and by FAPITEC/SE/FUNTEC/CNPq through the PPP Program 04/ 2011. FVR acknowledges FAPESP for the Post-Doctoral scholarship, Proc. No. 2013/20156–5.

supplementary crystallographic information

S1. Comment

Thiosemicarbazone derivatives have a wide range of biological properties. For example, some thiosemicarbazones similar to the title compound show antifungal activity (Nishimura et al., 1979). As part of our study on synthesis and structural chemistry of thiosemicarbazone derivatives from natural products, we report herein the crystal structure of a derivative of the essential oil of cinnamon bark (benzylideneacetone, a methyl derivative of the cinnamaldehyde).

In the crystal structure of the title compound the central N–N–C–N unit is not planar with an torsion angle along N1–N2–C10–N3 of -7.04 (16)° and the maximum deviation from the mean plane of the non-H atoms amounting to 0.2756 (6) Å for S1. The molecule, shows a trans conformation at the C7—C8 and N1—N2 bonds (Fig. 1).

In the crystal the molecules are linked by N—H···S hydrogen bonds interactions forming centrosymmetric dimers. Additionally, one weak N—H···N intramolecular H-interaction is observed.The crystal packing shows a herringbone arrangement viewed along the c-axis.(Fig. 3).

S2. Experimental

Starting materials were commercially available and were used without further purification. The title compound synthesis was adapted to a procedure reported previously (Freund & Schander, 1902). The hydrochloric acid catalyzed reaction, a mixture of benzylideneacetone (10 mmol) and 4-methyl-3-thiosemicarbazide (10 mmol) in ethanol (80 ml) was refluxed for 5 h. After cooling and filtering, the title compound was obtained. Crystals suitable for X-ray diffraction were obtained in ethanol by the slow evaporation of solvent.