(E)-2-(4-Benz­yloxy-2-hy­droxy­benzyl­idene)-N-phenyl­hydrazinecarbothio­amide

K Nisha; M Sithambaresan; M R Prathapachandra Kurup

doi:10.1107/S1600536811049658

. 2011 Nov 25;67(Pt 12):o3420. doi: 10.1107/S1600536811049658

(E)-2-(4-Benzyloxy-2-hydroxybenzylidene)-N-phenylhydrazinecarbothioamide

K Nisha ^a, M Sithambaresan ^b,^*, M R Prathapachandra Kurup ^a

PMCID: PMC3239056 PMID: 22199904

Abstract

The title compound, C₂₁H₁₉N₃O₂S, exists in the thione form. The configuration about the C=N bond is E. The hydrazinecarbothioamide unit adopts an almost planar arrangement, with maximum deviations of 0.016 (3) and −0.016 (2) Å for the two thiourea N atoms. An intramolecular O—H⋯N hydrogen bond occurs. Weak intermolecular N—H⋯S, C—H⋯O and C—H⋯π interactions are observed in the crystal structure.

Related literature

For applications of hydrazinecarbothioamide and its derivatives, see: Casas et al. (2000 ▶); Lukevics et al. (1995 ▶). For the synthesis, see: Joseph et al. (2004 ▶). For related hydrazinecarbothioamide structures, see: Seena et al. (2008 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₁H₁₉N₃O₂S
M _r = 377.45
Monoclinic,
a = 24.099 (3) Å
b = 16.173 (2) Å
c = 9.8370 (11) Å
β = 95.906 (7)°
V = 3813.5 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 296 K
0.30 × 0.25 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T _min = 0.945, T _max = 0.954
14236 measured reflections
3351 independent reflections
1848 reflections with I > 2σ(I)
R _int = 0.073

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.148
S = 1.01
3351 reflections
256 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) ▶; molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811049658/jj2110sup1.cif

e-67-o3420-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811049658/jj2110Isup2.hkl

e-67-o3420-Isup2.hkl^{(164.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811049658/jj2110Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the C16–C21 and C1–C6 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯N1	0.85 (4)	1.99 (4)	2.679 (3)	137 (4)
N2—H2B⋯S1ⁱ	0.85 (1)	2.55 (1)	3.392 (3)	170 (3)
C13—H13⋯O1ⁱⁱ	0.93	2.47	3.388 (4)	171
C5—H5⋯Cgⁱⁱⁱ	0.93	2.80	3.643 (4)	152
C12—H12⋯Cgⁱⁱ	0.93	2.87	3.741 (4)	157

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

Acknowledgments

KN is thankful to the Council of Scientific and Industrial Research, New Delhi, India, for financial support in the form of a Junior Research Fellowship. The authors are thankful to the Sophisticated Analytical Instrument Facility, Cochin University of Science & Technology, Kochi, India, for providing the single-crystal XRD data.

supplementary crystallographic information

Comment

Derivatives of hydrazinecarbothioamide are an important group of multidentate ligands with potential binding sites available for an extensive diversity of metal ions. A large number of studies have been devoted to the search for derivatives of hydrazinecarbothioamide, which have been used as drugs and have the ability to form complexes (Casas et al., 2000). These compounds find substantial applications in different aspects of modern scientific research (Lukevics et al., 1995).

The title compound (E)-2-[4-(benzyloxy)-2-hydroxybenzylidene]-N-\ phenylhydrazinecarbothioamide is found to exist in an E configuration having N3 and N1 atoms cis to each other with respect to C15–N2 bond (Fig. 1). The S1/C15/N12/N1 torsion-angle [-178.27 (19)°] suggests that the thionyl atom S1 is located trans to the azomethane nitrogen atom N1. The closeness of the C13═S1 bond distance [1.665 (3) Å] to the expected distance of a C═S bond (1.60 Å) (Allen et al., 1987; Seena et al., 2008) indicates that the compound exists in the thione form and it is further confirmed by the N1—N2 and N2—C15 bond distances. The hydrazinecarbothioamide moiety, (N1/N2/N3/C15/S1/C16), is nearly planar with a maximum deviation of 0.016 (3) and -0.016 (2) Å for atoms N3 and N2 from its least squares plane value. The three aromatic rings are twisted with a dihedral angle of 86.43 (17) Å between the least squares plane of the rings C1—C6 and C8—C13, 67.99 (19) Å between rings C1—C6 and C16—C21 and 29.77 (16) Å between rings C8—C13 and C16—C21, respectively.

An O2–H2A···N1 intramolecular hydrogen bond (Table 1), is observed which contributes to the planarity of the N1/C14/C11/C10/O2 group with a maximum deivation of 0.146 (2) Å for atom N1. Weak N—H···S, C—H···O and C—H···Cg π-ring intermolecular interactions (Table 1) are also observed.

Experimental

The title compound was prepared by adapting a reported procedure (Joseph et al., 2004) by refluxing a mixture of methanolic solutions of N-phenylhydrazinecarbothioamide (1.672 g, 10 mmol) and 4-(benzyloxy)-2-hydroxybenzaldehyde (2.282 g, 10 mmol) for four hours after adding 5 drops of acetic acid. Colorless crystals were collected, washed with few drops of methanol and dried over P₄O₁₀in vacuo. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation from its methanolic solution.