Crystal structure of (Z)-4-methylbenzyl 3-[1-(5-methylpyridin-2-yl)ethylidene]dithiocarbazate

Thahira Begum S A Ravoof; Edward R T Tiekink; Siti Aminah Omar; Sharifa Zaithun Begum; Mohamed I M Tahir

doi:10.1107/S205698901502407X

. 2015 Dec 19;71(Pt 12):o1071–o1072. doi: 10.1107/S205698901502407X

Crystal structure of (Z)-4-methylbenzyl 3-[1-(5-methylpyridin-2-yl)ethylidene]dithiocarbazate¹

Thahira Begum S A Ravoof ^a, Edward R T Tiekink ^b,^*, Siti Aminah Omar ^a, Sharifa Zaithun Begum ^a, Mohamed I M Tahir ^a

PMCID: PMC4719984 PMID: 26870503

Abstract

In the title dithiocarbazate compound, C₁₇H₁₉N₃S₂, the central CN₂S₂ residue is essentially planar (r.m.s. deviation = 0.0288 Å) and forms dihedral angles of 9.77 (8) and 77.47 (7)° with the substituted-pyridyl and p-tolyl rings, respectively, indicating a highly twisted molecule; the dihedral angle between the rings is 85.56 (8)°. The configuration about the C=N bond is Z, which allows for the formation of an intramolecular N—H⋯N(pyridyl) hydrogen bond. The packing features tolyl-methyl-C—H⋯N(imine), pyridyl-C—H⋯π(tolyl) and π–π interactions [between pyridyl rings with a distance = 3.7946 (13) Å], which generates jagged supramolecular layers that stack along the b axis with no directional interactions between them.

Keywords: crystal structure, hydrogen bonding, dithiocarbazate

Related literature

For the structure of the 4-methylpyridin-2-yl derivative, with an E configuration for the C=N bond, allowing for the formation of centrosymmetric {⋯HNCS}₂ synthons in the crystal, see: Omar et al. (2014 ▸). For the synthesis, see: Ravoof et al. (2010 ▸). graphic file with name e-71-o1071-scheme1.jpg

Experimental

Crystal data

C₁₇H₁₉N₃S₂
M _r = 329.47
Monoclinic,
a = 9.0073 (2) Å
b = 12.3856 (2) Å
c = 7.5553 (1) Å
β = 98.620 (2)°
V = 833.35 (3) Å³
Z = 2
Cu Kα radiation
μ = 2.88 mm⁻¹
T = 100 K
0.31 × 0.22 × 0.18 mm

Data collection

Agilent Xcalibur, Eos, Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▸) T _min = 0.43, T _max = 0.60
16118 measured reflections
3195 independent reflections
3191 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.081
S = 1.05
3195 reflections
205 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.30 e Å⁻³
Absolute structure: Flack x determined using 1558 quotients [(I ⁺)−(I ⁻)]/[(I ⁺)+(I ⁻)] (Parsons et al., 2013 ▸).
Absolute structure parameter: −0.011 (13)

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: SHELXL2014/7 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and DIAMOND (Brandenburg, 2006 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) 1, I. DOI: 10.1107/S205698901502407X/hb7554sup1.cif

e-71-o1071-sup1.cif^{(557.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901502407X/hb7554Isup2.hkl

e-71-o1071-Isup2.hkl^{(255.1KB, hkl)}

Click here for additional data file.^{(987.8KB, tif)}

. DOI: 10.1107/S205698901502407X/hb7554fig1.tif

The molecular structure of the title compound showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.

Click here for additional data file.^{(2.1MB, tif)}

a . DOI: 10.1107/S205698901502407X/hb7554fig2.tif

A view of the unit-cell contents in projection down the a axis. The tolyl-methyl-C—H⋯N(imine), pyridyl-C—H⋯π(tolyl) and π—π interactions are shown as orange, pink and orange dashed lines, respectively.

CCDC reference: 1442456

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

Cg1 is the centroid of the C3–C8 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N3	0.88 (2)	1.98 (3)	2.624 (3)	130 (3)
C12′—H12C⋯N2ⁱ	0.98	2.58	3.483 (3)	154
C13—H13⋯Cg1ⁱⁱ	0.95	2.76	3.582 (3)	145

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

Acknowledgments

This research was funded by Universiti Putra Malaysia (UPM) under Research University Grant Schemes (RUGS No. 9419400), the Fundamental Research Grant Scheme (FRGS No. 5524425) and the Science Fund (Science Fund No: 06–01-04-SF810). SAO wishes to thank the UPM for the award of a Graduate Research Fellowship.

supplementary crystallographic information

S1. Refinement

S2. Experimental

The precursor molecule, S-4-methylbenzyldithiocarbazate, was prepared by adapting the literature procedure of Ravoof et al. (2010). Thus, KOH (11.2 g, 0.2 mol) was dissolved in absolute ethanol (70 ml) and to this solution was added hydrazine hydrate (10 g, 0.2 mol) followed by cooling in an ice-salt bath. Drop wise addition of carbon disulfide (15.2 g, 0.2 mol) with constant stirring over 1 h followed. The two layers that subsequently formed were separated. The light-brown lower layer was dissolved in 40% ethanol (60 ml) below 268 K. The mixture was kept in an ice-bath and 4-methylbenzyl chloride (26.5 ml, 0.2 mol) was added drop wise with vigorous stirring. The major product, which was white and sticky was filtered and left overnight to dry over anhydrous silica gel in a desiccator. Recrystallization to yield analytically pure S-4-methylbenzyldithiocarbazate was achieved from hot acetonitrile. Yield: 82%; M.pt: 160–161 °C.

S-4-Methylbenzyldithiocarbazate (2.12 g, 0.01 mol) was dissolved in hot acetonitrile (100 ml) and added to an equimolar solution of 5-methyl-pyridine-2-aldehyde (1.21 g, 0.01 mol) in ethanol (25 ml). The mixture was then heated on a water bath until the volume has been reduced by half. A yellow precipitate formed after standing at room temperature for 1 h and this was washed with ethanol. Yellow prisms were deposited from its acetonitrile solution within a week. Yield: 78%. M.pt: 112–113 °C. Anal. Found (calc'd for C₁₇H₁₉N₃S₂): C, 62.32 (61.97); H, 5.59 (5.81); N 12.80 (12.75).