(2E)-2-(5-Bromo-2-hy­droxy-3-meth­oxy­benzyl­idene)-N-phenyl­hydrazine­carbo­thio­amide

Jinsa Mary Jacob; M Sithambaresan; M R Prathapachandra Kurup

doi:10.1107/S1600536812022520

. 2012 May 23;68(Pt 6):o1871–o1872. doi: 10.1107/S1600536812022520

(2E)-2-(5-Bromo-2-hydroxy-3-methoxybenzylidene)-N-phenylhydrazinecarbothioamide

Jinsa Mary Jacob ^a, M Sithambaresan ^b,^*, M R Prathapachandra Kurup ^a

PMCID: PMC3379435 PMID: 22719633

Abstract

The title compound, C₁₅H₁₄BrN₃O₂S, adopts an E,E conformation with respect to the azomethine and hydrazinic bonds and exists in the thioamide form. The two rings in the molecule are twisted away from each other, making a dihedral angle of 69.13 (13)°. In the crystal, molecules are linked through pairs of N—H⋯O and O—H⋯S hydrogen bonds, leading to the formation of inversion dimers which are stacked along the a axis. Intramolecular N—H⋯N, O—H⋯O and C—H⋯π interactions are also present.

Related literature

For applications of hydrazinecarbothioamide and its derivatives, see: Barber et al. (1992 ▶); Parrilha et al. (2011 ▶). For the synthesis, see: Joseph et al. (2006 ▶). For related structures, see: Dutta et al. (1997 ▶); Seena et al. (2006 ▶, 2008 ▶); Nisha et al. (2011 ▶); Jacob & Kurup (2012 ▶). For C=S and C=N double-bond lengths, see: Allen et al. (1987) ▶.

Experimental

Crystal data

C₁₅H₁₄BrN₃O₂S
M _r = 380.26
Triclinic,
a = 6.1046 (5) Å
b = 11.0329 (8) Å
c = 12.4303 (9) Å
α = 101.175 (3)°
β = 91.323 (2)°
γ = 104.759 (2)°
V = 791.91 (10) Å³
Z = 2
Mo Kα radiation
μ = 2.74 mm⁻¹
T = 296 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.399, T _max = 0.504
11624 measured reflections
2774 independent reflections
2338 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.068
S = 1.01
2774 reflections
212 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.44 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., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812022520/fj2553sup1.cif

e-68-o1871-sup1.cif^{(22.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812022520/fj2553Isup2.hkl

e-68-o1871-Isup2.hkl^{(136.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812022520/fj2553Isup3.cml

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

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

Cg2 is the centroid of the C9–C14 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3′⋯N1	0.83 (2)	2.25 (3)	2.654 (3)	110 (2)
N2—H2⋯O2ⁱ	0.84 (2)	2.23 (2)	2.983 (3)	149 (2)
O2—H2′⋯O1	0.82 (2)	2.20 (3)	2.631 (2)	113 (3)
O2—H2′⋯S1ⁱ	0.82 (2)	2.44 (2)	3.1547 (18)	146 (3)
C15—H15A⋯Cg2ⁱⁱ	0.96	2.90	3.649 (3)	135

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

Acknowledgments

The authors are grateful to the Sophisticated Analytical Instruments Facility, Cochin University of Science and Technology, Kochi-22, India for providing the single-crystal X-ray diffraction data. JMJ thanks the Council of Scientific and Industrial Research, New Delhi, India, for financial support in the form of a Senior Research Fellowship.

supplementary crystallographic information

Comment

The hydrazinecarbothioamides are envisaged as an important class of nitrogen-sulfur donor ligands because of their diverse chemical, biological and medicinal properties (Parrilha et al., 2011). The pharmacological activity of hydrazinecarbothioamides of o-hydroxyaromatic aldehydes is correlated to their ability to form chelates with biologically important metal ions by bonding through O, N and S atoms (Dutta et al., 1997).

The title compound adopts an E configuration with respect to the azomethine bond [N2—N1—C7—C6 = 174.8 (2)°] (Nisha et al., 2011). Also E configuration is perceived about C8—N2 bond (Fig. 1) similar to 5-bromo-3-methoxysalicylaldehyde-N(4)-cyclohexylthiosemicarbazone (Jacob & Kurup, 2012) but in contrast to 2-hydroxyacetophenone-N(4)-phenylthiosemicarbazone (Seena et al., 2006), where a Z configuration exists. This is confirmed by the N1—N2—C8—S1 torsion angle of 176.19 (18)°. Atom O1 lies cis to O2, with an O1—C4—C5—O2 torsion angle of -1.6 (3)° and atom N1 lies cis to N3, with an N1—N2—C8—N3 torsion angle of -5.9 (4)°. This favours the intramolecular hydrogen bonding interactions O2—H2'···O1 and N3—H3'···N1.

The C8—S1 bond distance [1.682 (2) Å] is closer to that expected for C═S bond length [1.60 Å] (Allen et al., 1987) which confirms the existence of the compound in the thioamido form in solid state. Also the C7—N1 bond distance [1.270 (3) Å] is appreciably close to that of a C═N double bond [1.28 Å] (Allen et al., 1987), confirming the azomethine bond formation.

The mean plane deviation calculations show that the molecule as a whole is non-planar. But the central hydrazinecarbothioamide group (C7/N1/N2/C8/S1/N3) is almost planar with a maximum deviation from the mean plane of 0.035 (2) Å for atom N2. This is similar to that observed in salicylaldehyde-N(4)-phenyl thiosemicarbazone (Seena et al., 2008). The planarity of hydrazinecarbothioamide moiety allows delocalization of the π electrons throughout the C7/N1/N2/C8/S1/N3 group. The ring Cg1ⁱⁱⁱ (comprising of atoms C1—C6, with a maximum deviation of -0.011 (2) Å for C2) makes a dihedral angle of 14.80 (10)° with the hydrazinecarbothioamide moiety while the two rings in the molecule are twisted away from each other by a dihedral angle of 69.13 (13)° [symmetry code:(iii) 2 - x, 1 - y, 1 - z].

Fig. 2 shows the packing diagram of the title compound. The crystal packing involves two types of intramolecular hydrogen bonding interactions (Table 1), O2—H2'···O1 and N3—H3'···N1 leading to the formation of five membered rings comprising of atoms C4, C5, O2, H2' and O1 and N2, C8, N3, H3' and N1 respectively. The intermolecular hydrogen bonds N2—H2···O2ⁱ and O2—H2'···S1ⁱ cause the pairing of molecules leading to the formation of centrosymmetric dimers in the crystal lattice. These dimers are stacked along the a axis. Further stabilization is provided by non-classical C7—H7···O2 and C15—H15A···Cg2ⁱⁱ interactions.

Experimental

The title compound was prepared by adapting a reported procedure (Joseph et al., 2006). To a methanolic (20 ml) solution of 4-phenylthiosemicarbazide (1 mmol, 0.1672 g), a methanolic (15 ml) solution of 5-bromo-3-methoxysalicylaldehyde (1 mmol, 0.2310 g) was added. The mixture was refluxed for 2 h in acid medium. After cooling, the compound formed was filtered off, washed with methanol and dried in vacuo. Yellow block shaped crystals suitable for single-crystal X-ray diffraction analysis were obtained by slow evaporation of its solution in 1:1 mixture of DMF and methanol over 3 days.