3-Methoxy­benzaldehyde thio­semi­carbazone

Jian Zhang; Lin-ping Wu; Ling-hua Zhuang; Guo-wei Wang

doi:10.1107/S160053680901040X

. 2009 Mar 28;65(Pt 4):o884. doi: 10.1107/S160053680901040X

3-Methoxybenzaldehyde thiosemicarbazone

Jian Zhang ^a, Lin-ping Wu ^a, Ling-hua Zhuang ^b, Guo-wei Wang ^a,^*

PMCID: PMC2968893 PMID: 21582593

Abstract

The title compound, C₉H₁₁N₃OS, was prepared by the reaction of 3-methoxybenzaldehyde and thiosemicarbazide. The benzylidene ring and the thiosemicarbazone fragment are slightly twisted, making a dihedral angle of 14.1 (1)°. A weak intramolecular N—H⋯N hydrogen bond may influence the conformation of the molecule. Intermolecular N—H⋯S hydrogen bonds build up a three-dimensional network.

Related literature

For a general background to thiosemicarbazone compounds, see: Casas et al. (2000 ▶); Tarafder et al. (2000 ▶); Ferrari et al. (2000 ▶); Deschamps et al. (2003 ▶); Maccioni et al. (2003 ▶); Chimenti et al.(2007 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₉H₁₁N₃OS
M _r = 209.27
Monoclinic,
a = 11.814 (2) Å
b = 5.6760 (11) Å
c = 15.248 (3) Å
β = 90.29 (3)°
V = 1022.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.908, T _max = 0.969
1946 measured reflections
1852 independent reflections
1494 reflections with I > 2σ(I)
R _int = 0.017
3 standard reflections every 200 reflections intensity decay: 9%

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.110
S = 1.06
1852 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680901040X/dn2432sup1.cif

e-65-0o884-sup1.cif^{(14.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901040X/dn2432Isup2.hkl

e-65-0o884-Isup2.hkl^{(89.3KB, hkl)}

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1ⁱ	0.86	2.57	3.370 (2)	156
N3—H3B⋯S1ⁱⁱ	0.86	2.57	3.411 (2)	166
N3—H3A⋯N1	0.86	2.25	2.611 (3)	105

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

supplementary crystallographic information

Comment

Thiosemicarbazones constitute an important class of N,S donor ligands due to their propensity to react with a wide range of metals (Casas et al., 2000). Thiosemicarbazones exhibit various biological activities and have therefore attracted considerable pharmaceutical interest (Maccioni et al., 2003; Ferrari et al., 2000). They have been evaluated as antiviral, antibacterial and anticancer therapeutics. Thiosemicarbazones belong to a large group of thiourea derivatives, whose biological activities are a function of parent aldehyde or ketone moiety (Chimenti et al., 2007). Schiff bases show potential as antimicrobial and anticancer agents (Tarafder et al., 2000; Deschamps et al., 2003) and so have biochemical and pharmacological applications. We here report the crystal structure of the title compound (I).

The sulfur atom and the hydrazine nitrogen N1 are in trans position with respect to the C9–N2 bond. This conformation may be induced by the weak intramolecular N-H···N hydrogen bond (Fig. 1, Table 1). All bond lengths are within normal ranges (Allen et al., 1987).

At first glance the molecule is roughly planar with the largest deviation from the mean plane being -0.272 (3) Å at N3, however the benzaldehyde ring and the thiosemicarbazone fragment are twisted with respect to each other making a dihedral angle of 14.1 (1)°.

The molecules are connected by intermolecular N—H···S hydrogen bonds which build up a three dimensional network (Table 1, Fig.2).

Experimental

A mixture of 3-methoxybenzaldehyde (1.36 g, 0.01 mol) and hydrazinecarbothioamide (0.91 g, 0.01 mol) in 20 ml of absolute methanol was refluxed for about 3 h. On cooling, the solid separated was filtered and recrystallized from ethyl acetate. Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of ethyl acetate. ¹H NMR (DMSO, δ, p.p.m.) 11.39 (s, 1 H), 8.17 (s, 1 H), 8.02 (s,2 H), 7.42 (m, 1 H), 7.30 (t, 2 H), 6.99 (t,1 H), 3.79 (t, 3 H).