2-[1-(2-Hy­droxy-4-meth­oxy­phen­yl)ethyl­idene]-N-methyl­hydrazinecarbo­thio­amide

Brian J Anderson; Michael B Freedman; Sean P Millikan; Jerry P Jasinski

doi:10.1107/S1600536813019831

. 2013 Jul 24;69(Pt 8):o1315. doi: 10.1107/S1600536813019831

2-[1-(2-Hydroxy-4-methoxyphenyl)ethylidene]-N-methylhydrazinecarbothioamide

Brian J Anderson ^a, Michael B Freedman ^a, Sean P Millikan ^a, Jerry P Jasinski ^a,^*

PMCID: PMC3793802 PMID: 24109389

Abstract

In the title compound, C₁₁H₁₅N₃O₂S, the dihedral angle between the mean planes of the benzene ring and hydrazinecarbothioamide group is 9.2 (1)°. An intramolecular O—H⋯N hydrogen bond is observed, serving to maintain an approximately planar conformation for the molecule. In the crystal, inversion dimers linked by C—H⋯O interactions occur. Further C—H⋯O contacts link dimers into (010) chains.

Related literature

For the synthesis and structure of thiosemicarbazones as ligands, see: Lobana et al. (2009 ▶, 2012 ▶). For palladium complexes with thiosemicarbazone ligands, see: Chellan et al. (2010 ▶). For related structures, see: Anderson et al. (2012 ▶, 2013 ▶). For bond lengths, see: Allen et al. (1987 ▶). graphic file with name e-69-o1315-scheme1.jpg

Experimental

Crystal data

C₁₁H₁₅N₃O₂S
M _r = 253.32
Monoclinic,
a = 10.9881 (8) Å
b = 9.1468 (6) Å
c = 12.5575 (9) Å
β = 109.400 (8)°
V = 1190.45 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 173 K
0.42 × 0.38 × 0.14 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T _min = 0.728, T _max = 1.000
13894 measured reflections
4104 independent reflections
3320 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.076
wR(F ²) = 0.231
S = 1.16
4104 reflections
158 parameters
H-atom parameters constrained
Δρ_max = 1.21 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813019831/hg5331sup1.cif

e-69-o1315-sup1.cif^{(21.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813019831/hg5331Isup2.hkl

e-69-o1315-Isup2.hkl^{(225.1KB, hkl)}

Click here for additional data file.^{(4.8KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813019831/hg5331Isup3.cml

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
O1—H1⋯N1	0.82	1.85	2.566 (3)	145
C10—H10A⋯O2ⁱ	0.96	2.59	3.301 (4)	132
C10—H10C⋯O1ⁱⁱ	0.96	2.57	3.481 (4)	158

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

Acknowledgments

JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

Comment

Thiosemicarbazones are a versatile class of ligands that can adopt multiple modes of binding to a metal (Lobana, et al., 2009) and the synthesis and structure determination of these metal complexes is an active area of research. (Lobana, et al., 2012) Palladium complexes with thiosemicarbazone ligands have been shown to have a variety of biological activity including anti-fungal and anti-tumor activity. (Chellan, et al., 2010). We have previously reported the structure of two analogous novel thiosemicarbazones (Anderson, et al., 2012; Anderson, et al., 2013). Here, we report the synthesis and crystal structure of a novel thiosemicarbazone ligand, (I), C₁₁H₁₅N₃O₂S .

In (I), the dihedral angle between the mean planes of the benzene ring and hydrazinecarbothioamide group (N1/N2/C8/S1/N3) is 9.2 (1)° (Fig. 1). Bond lengths are in normal ranges (Allen et al., 1987). In the crystal, an intramolecular O—H···N hydrogen bond is observed serving to keep the molecule in a nearly planar conformation. Additional weak and C—H···O intermolecular interactions (Table 1) assist in linking the molecules into dimers along (010) and influence crystal packing (Fig. 2).

Experimental

A 50 mL round bottom flask was charged with 0.218 g (1.31 mmol) of 2'-hydroxy-4'-methoxyacetophenone, 0.138 g (1.31 mmol) of 4-methyl-3- thiosemicarbazide, dissolved in 20 mL of methanol. The resulting colorless solution was refluxed for 48 hours and then a drop of concentrated HCl was added and the solution was refluxed for an additional 48 hours. The resulting yellow solution was transferred to a 125 mL separatory funnel. Dichloromethane (10 mL) and water (10 mL) were added, and the organic layer was separated. The aqueous layer was extracted with an additional 10 mL of dichloromethane. The organic layers were combined, washed with brine (2 x 10 mL), dried with magnesium sulfate, and the solvent was removed in vacuo to give a yellow solid (Fig. 3). The solid was dissolved in hot acetonitrile, allowed to cool to room temperature and then stored at 273 K resulting in colorless crystals (58 mg, 18%) after 24 hours. M.p. 448-453 K.