4-Hy­droxy-3-meth­oxy­benzaldehyde 4-ethyl­thio­semicarbazone

Adriano Bof de Oliveira; Johannes Beck; Jörg Daniels; Bárbara Regina Santos Feitosa

doi:10.1107/S1600536814016018

. 2014 Jul 17;70(Pt 8):o868. doi: 10.1107/S1600536814016018

4-Hydroxy-3-methoxybenzaldehyde 4-ethylthiosemicarbazone

Adriano Bof de Oliveira ^a,^*, Johannes Beck ^b, Jörg Daniels ^b, Bárbara Regina Santos Feitosa ^a

PMCID: PMC4158485 PMID: 25249915

Abstract

In the crystal structure of the title compound, C₁₁H₁₅N₃O₂S, the C—N—N—C and C—N—C—C torsion angles involving the benzene ring and ethyl group are 11.91 (15) and 99.4 (2)°, respectively. An intramolecular N—H⋯N hydrogen bond is observed. In the crystal, molecules are linked via N—H⋯O and N—H⋯S hydrogen bonds into a three-dimensional hydrogen bonded network. Finally, the molecules show a herringbone arrangement when viewed along the a axis.

Keywords: Synthesis thiosemicarbazones, biological properties of thiosemicarbazones., crystal structure

Related literature

For the synthesis and biological applications of thiosemicarbazone derivatives, see: Lovejoy & Richardson (2008 ▶). For one of the first reports on the synthesis of thiosemicarbazone derivatives, see: Freund & Schander (1902 ▶).

Experimental

Crystal data

C₁₁H₁₅N₃O₂S
M _r = 253.32
Orthorhombic,
a = 8.9962 (2) Å
b = 16.1159 (2) Å
c = 8.5491 (1) Å
V = 1239.46 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 293 K
0.15 × 0.13 × 0.12 mm

Data collection

Nonius Kappa CCD diffractometer
Absorption correction: multi-scan (Blessing, 1995 ▶) T _min = 0.939, T _max = 0.990
22619 measured reflections
2837 independent reflections
2590 reflections with I > 2σ(I)
R _int = 0.050

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.071
S = 1.01
2837 reflections
214 parameters
1 restraint
All H-atom parameters refined
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ▶)
Absolute structure parameter: 0.03 (6)

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: HKL, 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/S1600536814016018/bx2462sup1.cif

e-70-0o868-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814016018/bx2462Isup2.hkl

e-70-0o868-Isup2.hkl^{(139.3KB, hkl)}

Click here for additional data file.^{(4.7KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814016018/bx2462Isup3.cml

CCDC reference: 1013029

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
O2—HO2⋯S1ⁱ	0.86 (3)	2.26 (3)	3.1144 (14)	173 (2)
N3—HN3⋯N1	0.77 (2)	2.25 (2)	2.643 (2)	112.4 (19)
N3—HN3⋯O2ⁱⁱ	0.77 (2)	2.43 (2)	3.023 (2)	135 (2)
N3—HN3⋯O1ⁱⁱ	0.77 (2)	2.52 (2)	3.061 (2)	128.3 (19)

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

Acknowledgments

We gratefully acknowledge financial support by the German Research Foundation (DFG) through the Collaborative Research Center SFB 813, Chemistry at Spin Centers. BRSF acknowledges the CNPq/UFS for the award of a PIBIC scholarship.

supplementary crystallographic information

S1. Related Literature

For Biological activities of thiosemicarbazone derivatives see Lovejoy & Richardson, 2008.

S2. Comment

Thiosemicarbazone derivatives have a wide range of biological properties. For example, some thiosemicarbazones show anti-proliferative activity against tumor cells (Lovejoy & Richardson, 2008). 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 vanillin.

In the title compound, C₁₁H₁₅N₃O₂S, Fig. 1, the C-N-N-C and C–N–C–C fragments makes torsion angles of 11.91 (15)° and 99.4 (2)° with the benzene ring and ethyl group respectively. The molecule matches the asymmetric unit (Fig. 1) and shows a trans conformation at the C7—N1 and N1—N2 bonds. In the crystal structure the molecules are linked via N—H···O and O—H···S hydrogen bonds interactions into a crystal packing which shows a herringbone arrangement viewed along the a-axis,Fig.2. Additionally, one N—H···N intramolecular hydrogen bond interactions is observed, Table 1,

S3. Experimental

Starting materials were commercially available and were used without further purification. The synthesis of the title compound was adapted to a procedure reported previously (Freund & Schander, 1902). In a hydrochloric acid catalyzed reaction, a mixture of vanillin (10 mmol) and 4-ethyl-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.