N′-[Bis(benzyl­sulfan­yl)methyl­idene]benzohydrazide

Shahedeh Tayamon; Thahira Begum S A Ravoof; Mohamed Ibrahim Mohamed Tahir; Karen A Crouse; Edward R T Tiekink

doi:10.1107/S1600536812019472

. 2012 May 5;68(Pt 6):o1640–o1641. doi: 10.1107/S1600536812019472

N′-[Bis(benzylsulfanyl)methylidene]benzohydrazide

Shahedeh Tayamon ^a, Thahira Begum S A Ravoof ^a, Mohamed Ibrahim Mohamed Tahir ^a, Karen A Crouse ^a,^‡, Edward R T Tiekink ^b,^*

PMCID: PMC3379243 PMID: 22719441

Abstract

In the title hydrazonodithioate, C₂₁H₁₉N₃OS₂, the amide group is twisted out of the plane through the S₂C=N atoms: the C—N—N—C torsion angle is 139.71 (13)°. The pyridine ring forms dihedral angles of 52.96 (8) and 86.46 (8)° with the phenyl rings, and the latter are approximately orthogonal [dihedral angle = 76.42 (9)°]. Supramolecular chains sustained by N—H⋯O hydrogen bonds and propagated by glide symmetry along the c axis are found in the crystal structure. The chains are consolidated into a three-dimensional architecture by C—H⋯O and C—H⋯N interactions.

Related literature

For background to the coordination chemistry of dithiocarbazate derivatives, see: Tarafder et al. (2002 ▶); Ravoof et al. (2010 ▶). For related syntheses, see: Ali & Tarafder (1977 ▶); Ali et al. (2001 ▶); Manan et al. (2012 ▶). For related structures, see: Jasinski et al. (2010 ▶); Singh et al. (2007 ▶). graphic file with name e-68-o1640-scheme1.jpg

Experimental

Crystal data

C₂₁H₁₉N₃OS₂
M _r = 393.51
Monoclinic,
a = 11.2593 (4) Å
b = 21.2182 (7) Å
c = 8.6041 (3) Å
β = 103.678 (3)°
V = 1997.24 (12) Å³
Z = 4
Cu Kα radiation
μ = 2.54 mm⁻¹
T = 150 K
0.50 × 0.36 × 0.16 mm

Data collection

Agilent Xcaliber Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.42, T _max = 0.67
38338 measured reflections
3867 independent reflections
3715 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.097
S = 1.03
3867 reflections
247 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812019472/hb6755sup1.cif

e-68-o1640-sup1.cif^{(20.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812019472/hb6755Isup2.hkl

e-68-o1640-Isup2.hkl^{(185.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812019472/hb6755Isup3.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
N2—H2N⋯O1ⁱ	0.864 (17)	1.936 (17)	2.7852 (15)	167.4 (16)
C7—H7⋯N3ⁱⁱ	0.95	2.54	3.339 (2)	142
C8—H8⋯N3ⁱⁱⁱ	0.95	2.52	3.424 (2)	158
C18—H18⋯O1ⁱ	0.95	2.53	3.365 (2)	147

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

Acknowledgments

Support for the project came from Universiti Putra Malaysia (UPM) under their Research University Grant Scheme (RUGS No. 9174000), the Malaysian Ministry of Science, Technology and Innovation (grant No. 09-02-04-0752-EA001) and the Malaysian Fundamental Research Grant Scheme (FRGS No. 01-13-11-986FR). We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (grant No. UM.C/HIR/MOHE/SC/12).

supplementary crystallographic information

Comment

Our interest in investigating the coordination properties of ligands containing the H—N—C═S moiety (Tarafder et al., 2002; Ravoof et al., 2010) and our desire to expand the study of this class of biologically important compounds has lead us to synthesize a series of related ligands (Ali et al., 2001; Manan et al., 2012). The title compound N'-bis(benzylsulfanyl)methylidene]benzohydrazide, (I), was obtained from an attempt to prepare S-benzyl isonicotinoylcarbonohydrazonodithioate (see Experimental).

In (I), Fig. 1, the amide is twisted out of the plane through the S₂C═N atoms with the C1—N1—N2—C16 torsion angle being 139.71 (13)°. A similar twist was found in the structure of (PhCH₂S)₂C═ NN(H)C(═ O)C₆H₄OMe-4 (Jasinski et al., 2010) but a planar arrangement was observed in the structure of (PhCH₂S)₂C═NN(H)C(═O)C₆H₄OMe-2 (Singh et al., 2007). The dihedral angle between the phenyl rings is 76.42 (9)°, indicating an almost orthogonal relationship. Each of these rings forms a dihedral angle of 52.96 (8) and 86.46 (8)° with the pyridyl ring.

The crystal packing features supramolecular chains sustained by N—H···O hydrogen bonds, Table 1, and propagated by glide symmetry along the c axis, Fig. 2. Chains are consolidated into a three-dimensional architecture by C—H···O and C—H···N interactions, Fig. 3 and Table 1.

Experimental

The procedure to synthesize S-benzyldithiocarbazate (Ali & Tarafder, 1977) was adapted to prepare S-benzyl isonicotinoylcarbonohydrazono dithioate by replacing hydrazine with its isonicotinic acid derivative. Potassium hydroxide (0.2 mol, 11.2 g) in absolute ethanol (70 ml) was added to a suspension of isonicotinic acid hydrazide (0.2 mol, 27.43 g) in absolute ethanol (700 ml). The pale-yellow solution was kept in an ice-salt bath and carbon disulfide (0.2 mol) was added drop-wise with constant stirring over one hour. Benzylchloride (0.2 mol, 23 ml) was then added drop-wise with vigorous stirring to the pale-orange solution obtained above. The reaction temperature was maintained below 278 K. An unidentified pale-yellow solid (33.84 g) which did not contain any benzyl substituent was filtered from the mixture. The filtrate was kept in a freezer for one week before it was used as replacement for absolute ethanol to repeat the above reaction. The final solution produced dark-yellow blocks of the title compound after storage at 268 K for 5 months. (Yield 16 g; M.pt: 369 K).