(Pyridin-4-yl)methyl N′-(3-phenyl­allyl­idene)hydrazinecarbodithio­ate

May Lee Low; Thahira Begum S A Ravoof; Mohamed Ibrahim Mohamed Tahir; Karen A Crouse; Edward R T Tiekink

doi:10.1107/S1600536812051537

. 2013 Jan 4;69(Pt 2):o167–o168. doi: 10.1107/S1600536812051537

(Pyridin-4-yl)methyl N′-(3-phenylallylidene)hydrazinecarbodithioate

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

PMCID: PMC3569232 PMID: 23424455

Abstract

In the title compound, C₁₆H₁₅N₃S₂, the central C₂N₂S₂ residue is planar (r.m.s. deviation = 0.045 Å) and the pyridyl and benzene rings are inclined and approximately coplanar to this plane, respectively [dihedral angles = 72.85 (9) and 10.73 (9)°], so that, overall, the molecule adopts an L-shape. The conformation about each of the N=C [1.290 (3) Å] and C=C [1.340 (3) Å] bonds is E. Supramolecular chains along [1-10] are stabilized by N—H⋯N(pyridine) hydrogen bonding and these are connected into a double layer that stacks along the c-axis direction by C—H⋯π(pyridine) interactions.

Related literature

For background to related Schiff bases of S-substituted dithiocarbazates with cinnamaldehyde, see: Tarafder et al. (2008 ▶, 2010 ▶). For the corresponding metal complexes, see: Reza et al. (2012 ▶); Liu et al. (2009 ▶). For the biological activity of similar sulfur–nitrogen-containing Schiff base derivatives, see: Maia et al. (2010 ▶); Pavan et al. (2010 ▶); Zhu et al. (2009 ▶). For the synthesis, see: Crouse et al. (2004 ▶); Khoo (2008 ▶); Tarafder et al. (2008 ▶, 2010 ▶).

Experimental

Crystal data

C₁₆H₁₅N₃S₂
M _r = 313.43
Triclinic,
a = 5.3784 (5) Å
b = 10.1570 (9) Å
c = 14.5488 (17) Å
α = 77.315 (9)°
β = 84.735 (9)°
γ = 78.193 (8)°
V = 758.06 (13) Å³
Z = 2
Cu Kα radiation
μ = 3.14 mm⁻¹
T = 100 K
0.13 × 0.06 × 0.01 mm

Data collection

Oxford Diffraction Xcaliber Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.83, T _max = 0.97
15664 measured reflections
2918 independent reflections
2469 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.115
S = 1.05
2918 reflections
193 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.29 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 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(17.9KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812051537/qm2090sup1.cif

e-69-0o167-sup1.cif^{(17.9KB, cif)}

Click here for additional data file.^{(140.3KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812051537/qm2090Isup2.hkl

e-69-0o167-Isup2.hkl^{(140.3KB, hkl)}

Click here for additional data file.^{(5.6KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812051537/qm2090Isup3.cml

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

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

Cg1 is the centroid of the N3,C12–C15 pyridyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯N3ⁱ	0.88 (2)	2.02 (2)	2.897 (3)	172 (2)
C8—H8⋯Cg1ⁱⁱ	0.95	2.92	3.701 (3)	141

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

Acknowledgments

Support for this project came from Universiti Putra Malaysia (UPM) under their Research University Grant Scheme (RUGS 9174000) and the Malaysian Ministry of Science Technology and Innovation (MOSTI 09–02-04–9752EA001) and the Malaysian Fundamental Research Grant Scheme (FRGS 01–13-11–986FR). We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/12).

supplementary crystallographic information

Comment

Schiff bases of S-substituted dithiocarbazates with cinnamaldehyde attract interest in terms of both coordination chemistry (Reza et al., 2012; Liu et al., 2009) and for their biological activities (Maia et al., 2010; Pavan et al., 2010; Zhu et al., 2009. In pursuing our continuing interest in the coordination chemistry of dithiocarbazate derivatives and their biological importance (Tarafder et al., 2010; Tarafder et al., 2008), the title compound, (I), the product of condensation between S-4-picolyl dithiocarbazate and cinnamaldehyde, was investigated.

In (I), Fig. 1, the central C₂N₂S₂ residue is planar (r.m.s. deviation = 0.045 Å) with maximum deviations of 0.040 (2) Å for each of N1 and C11, and -0.048 (1) Å for the S1 atom. The pyridyl ring is inclined to this plane, forming a dihedral angle of 72.85 (9) °, whereas the benzene ring is almost co-planar [dihedral angle = 10.73 (9)°]. The maximum twist from co-planarity along the C₅N₂ chain is seen in the C1—N1—N2—C2 torsion angle of -176.15 (19) Å. The amine-N1—H atom is syn to the thione-S2 atom. The conformation about each of the N2═C2 [1.290 (3) Å] and C3═C4 [1.340 (3) Å] bonds is E. Globally, the molecule adopts an L-shape as the pyridyl residue is anti to the thione-S2 atom. A very similar conformation was found in the benzyl ester (Tarafder et al., 2008).

The pyridyl ring proves pivotal in the crystal packing by forming a hydrogen bond with the amine-N1—H atom and acting as an acceptor in a C—H···π(pyridyl) contact, Table 1. The hydrogen bonding leads to the formation of supramolecular chains along [1 1 0] and these are connected into a double layer in the ab plane via the C—H···π(pyridyl) contacts, Fig. 2.

Experimental

The previously reported method for preparation substituted dithiocarbazate (Crouse et al., 2004) was modified by reaction with 4-picolylchloride hydrochloride (Khoo, 2008).

Potassium hydroxide (11.4 g, 0.2 mol) was dissolved completely in 90% ethanol (70 ml) and the mixture was cooled in ice. To the cold solution, hydrazine hydrate (9.7 ml, 0.2 mol) was added slowly with stirring. Carbon disulfide (12.0 ml, 0.2 mol) was then added drop-wise with vigorous stirring for about 1 h. The temperature of the reaction mixture was kept below 268 K during addition. During this time two layers formed. The resulting yellow oil (lower layer) was separated and dissolved in 40% ethanol (60 ml). 4-Picolylchloride hydrochloride (32.8 g, 0.2 mol) was completely dissolved in 100 ml of 80% ethanol and added slowly to the above solution with vigorous mechanical stirring. The resulting white product (S4PDTC) was separated by filtration, washed with water and dried. The crude product was recrystallized from absolute ethanol.

Previously reported methods for preparation of Schiff bases (Tarafder et al., 2010; Tarafder et al., 2008) were used to prepare S4PDTC derivatives with cinnamaldehyde. An equimolar amount of cinnamaldehyde (1.26 ml) was added to the solution of S4PDTC (1.99 g, 0.01 mol) dissolved in hot absolute ethanol (100 ml). The mixture was heated while being stirred to reduce it to half the original volume and then cooled. The orange compound was filtered, washed with absolute ethanol then dried over silica gel. Single crystals were obtained after recrystallization from a mixture of DMF/chloroform. (yield 72%, M.pt: 481–482 K).