N-Ethyl-2-[1-(2-hy­droxy-4-methyl­phen­yl)ethyl­idene]hydrazinecarbo­thio­amide

Brian J Anderson; Jeffrey R Hall; Jerry P Jasinski

doi:10.1107/S1600536814012203

. 2014 May 31;70(Pt 6):o735. doi: 10.1107/S1600536814012203

N-Ethyl-2-[1-(2-hydroxy-4-methylphenyl)ethylidene]hydrazinecarbothioamide

Brian J Anderson ^a, Jeffrey R Hall ^a, Jerry P Jasinski ^a,^*

PMCID: PMC4051077 PMID: 24940300

Abstract

The title compound, C₁₂H₁₇N₃OS, crystallizes with two independent molecules (A and B) in the asymmetric unit. The dihedral angle between the mean planes of the benzene ring and the hydrazinecarbothioamide group are 6.9 (4) and 37.2 (5)° in molecules A and B, respectively. An intramolecular O—H⋯N hydrogen bond is observed in each molecule. This serves to maintain an approximately planar conformation for molecule A, but leaves a significant twist between these two groups in molecule B. In the crystal, a weak N—H⋯S interaction is observed, forming inversion dimers among the B molecules and resulting in an R ₂ ²(8) motif. These dimers are further interconnected by weak N—H⋯O and C—H⋯O intermolecular interactions, forming chains along [011].

Related literature

For the biological activity of thiosemicarbazones, see: Chellan et al. (2010 ▶). For binding motifs of thiosemicarbazones, see: Lobana et al. (2009 ▶). For thiosemicarbazones as ligands in catalysis, see: Xie et al. (2010 ▶). For related structures, see: Anderson et al. (2012 ▶, 2013a ▶,b ▶). graphic file with name e-70-0o735-scheme1.jpg

Experimental

Crystal data

C₁₂H₁₇N₃OS
M _r = 251.34
Triclinic,
a = 7.4253 (4) Å
b = 8.7713 (4) Å
c = 20.7093 (11) Å
α = 96.238 (4)°
β = 94.400 (5)°
γ = 100.177 (4)°
V = 1313.35 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 173 K
0.28 × 0.24 × 0.12 mm

Data collection

Agilent Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T _min = 0.693, T _max = 1.000
17011 measured reflections
8692 independent reflections
5875 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.070
wR(F ²) = 0.204
S = 1.09
8692 reflections
315 parameters
H-atom parameters constrained
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.38 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 ▶; Palatinus & van der Lee, 2008 ▶; Palatinus et al., 2012 ▶).; 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) I. DOI: 10.1107/S1600536814012203/fj2676sup1.cif

e-70-0o735-sup1.cif^{(32.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814012203/fj2676Isup2.hkl

e-70-0o735-Isup2.hkl^{(476KB, hkl)}

Click here for additional data file.^{(4.9KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814012203/fj2676Isup3.cml

CCDC reference: 1005355

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
O1A—H1A⋯N3A	0.84	1.85	2.589 (2)	146
C10A—H10B⋯O1B ⁱ	0.98	2.45	3.406 (3)	164
O1B—H1B⋯N3B	0.84	1.81	2.545 (2)	146
N1B—H1BA⋯O1A ⁱⁱ	0.88	2.36	3.076 (2)	139
N2B—H2B⋯S1B ⁱⁱⁱ	0.88	2.52	3.320 (2)	152

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

Acknowledgments

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

supplementary crystallographic information

1. Comment

Thiosemicarbazones are a versatile class of ligands that have been studied for their biological activity (Chellan et al., 2010), interesting binding motifs (Lobana et al., 2009), and their use as ligands in catalysis (Xie et al., 2010). We have previously reported the structure of three similar novel thiosemicarbazones (Anderson et al., 2012; Anderson et al., 2013a; Anderson et al., 2013b). Here, we report the synthesis and crystal structure of a new novel thiosemicarbazone ligand, (I), C₁₂H₁₇N₃OS.

The title compound, (I), crystallizes with two independent molecules (A & B) in the asymmetric unit (Fig. 1). The dihedral angles between the mean planes of the benzene ring and the hydrazinecarbothioamide group is 6.9 (4)° (N3A/N2A/C1A/S1A/N1A) and 37.2 (5)° (N3B/N2B/C1B/S1B/N1B). An intramolecular O—H···N hydrogen bond is observed serving to maintain an approximately planar conformation in A. However in B there is a significant twist between these two groups. In the crystal, a weak N2B—H2B···S1B intermolecular interaction is observed forming inversion dimers among the B molecules in an R₂²[8] motif format (Fig. 2). These dimers are further interconnected by weak N1B—H1BA···O1A and C10A—HH10B···O1B intermolecular interactions (Table 1) forming polymeric chains along [011].

2. Experimental

A 25 mL round bottom flask was charged with 0.1986 g (1.428 mmol) of 4'-methylacetophenone, 0.1702 g (1.428 mmol) of 4-ethyl-3-thiosemicarbazide and dissolved in 5 mL of a 1:1 ethanol: water solution and refluxed for 96 hours (Fig. 3). The reaction was allowed to cool to room temperature before dichloromethane (5 mL) and deionized water (5mL) were added, and the organic layer was separated. The aqueous layer was then extracted with an additional 5 mL of dichloromethane. The organic layers were then combined, washed with brine (2 X 5 mL), dried with magnesium sulfate, and the solvent removed in vacuo resulting in an off-white powder. The product was recrystallized from dichloromethane. m.p. 428–431 K.