Crystal structure of 4-methyl­benzyl N′-[(thio­phen-2-yl)methyl­idene]hydrazinecarbodi­thio­ate

Syahirah binti Ramli; Thahira Begum S A Ravoof; Mohamed Ibrahim Mohamed Tahir; Edward R T Tiekink

doi:10.1107/S205698901501107X

. 2015 Jun 13;71(Pt 7):o475–o476. doi: 10.1107/S205698901501107X

Crystal structure of 4-methylbenzyl N′-[(thiophen-2-yl)methylidene]hydrazinecarbodithioate

Syahirah binti Ramli ^a,^*, Thahira Begum S A Ravoof ^a,^*, Mohamed Ibrahim Mohamed Tahir ^a, Edward R T Tiekink ^b

PMCID: PMC4518925 PMID: 26279916

Abstract

In the title compound, C₁₅H₁₆N₂S₃ {systematic name: [({[(4-methylphenyl)methyl]sulfanyl}methanethioyl)amino][1-(thiophen-2-yl)ethylidene]amine}, the central CN₂S₂ residue is almost planar (r.m.s. deviation = 0.0061 Å) and forms dihedral angles of 7.39 (10) and 64.91 (5)° with the thienyl and p-tolyl rings, respectively; the dihedral angle between these rings is 57.52 (6)°. The non-thione S atoms are syn, and with respect to the thione S atom, the benzyl group is anti. In the crystal, centrosymmetrically related molecules self-associate via eight-membered {⋯HNCS}₂ synthons. The dimeric aggregates stack along the a axis and are are consolidated into a three-dimensional architecture via methyl-C—H⋯π(benzene) and benzene-C—H⋯π(thienyl) interactions.

Keywords: crystal structure, hydrogen bonding, dithiocarbazate, C—H⋯π interactions

Related literature

For the structure of the parent compound, in which the benzyl residue is syn to the thione S atom, see: Chan et al. (2003 ▸). For the synthesis, see: Tarafder et al. (2002 ▸). graphic file with name e-71-0o475-scheme1.jpg

Experimental

Crystal data

C₁₅H₁₆N₂S₃
M _r = 320.48
Monoclinic,
a = 5.6956 (4) Å
b = 14.3424 (9) Å
c = 18.9255 (11) Å
β = 90.263 (5)°
V = 1545.98 (17) Å³
Z = 4
Cu Kα radiation
μ = 4.30 mm⁻¹
T = 150 K
0.15 × 0.10 × 0.06 mm

Data collection

Oxford Diffraction Xcaliber Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▸) T _min = 0.774, T _max = 1.000
8463 measured reflections
2830 independent reflections
2506 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.109
S = 1.06
2830 reflections
186 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.33 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, 2015 ▸); program(s) used to refine structure: SHELXL2014 (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/S205698901501107X/hb7439sup1.cif

e-71-0o475-sup1.cif^{(302.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901501107X/hb7439Isup2.hkl

e-71-0o475-Isup2.hkl^{(226.4KB, hkl)}

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S205698901501107X/hb7439fig1.tif

The molecular structure of the title compound showing displacement ellipsoids at the 70% probability level.

Click here for additional data file.^{(1MB, tif)}

. DOI: 10.1107/S205698901501107X/hb7439fig2.tif

Overlay diagram of the title compound (red image) with the parent compound (blue). The molecules have been overlapped so that the thienyl residues are coincident.

Click here for additional data file.^{(1.4MB, tif)}

a . DOI: 10.1107/S205698901501107X/hb7439fig3.tif

A view of the unit-cell contents in projection down the a axis. The N—H⋯S (orange) and C—H⋯π (purple) interactions are shown as dashed lines.

CCDC reference: 1405284

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

Table 1. Hydrogen-bond geometry (, ).

Cg1 and Cg2 are the centroids of the S3,C3C6 and C8C13 rings, respectively.

DHA	DH	HA	D A	DHA
N1H1NS2ⁱ	0.87(2)	2.57(2)	3.4433(18)	176(3)
C2H22Cg2ⁱⁱ	0.98	2.85	3.616(3)	138
C12H12Cg1ⁱⁱⁱ	0.95	2.89	3.560(2)	130

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

Acknowledgments

The 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). SR thanks the UPM for the award of a Graduate Research Fellowship.

supplementary crystallographic information

S1. Experimental

The title compound was prepared as per a reported procedure (Tarafder et al., 2002). The light-yellow precipitate formed was filtered off and recrystallized from its acetonitrile solution as yellow prisms. Yield 56%; M.pt: 175–177 °C. Anal. Calcd for C₁₅H₁₆N₂S₃: C, 56.21; H, 5.03; N, 8.74. Found: C, 55.97; H, 4.96; N, 8.10. IR (cm^-1, FT—IR): 3143 w, 1511 m, 1060 m, 924 s. ¹H-NMR: (DMSO-d₆, p.p.m.) δ: 12.42 (s, 1H, NH), 7.24–7.55 (multiplet, 4H, Ar–H), 7.03–7.10 (multiplet, 3H, thiophene-H), 4.37 (s, 2H, –SCH₂), 2.24, 2.36 (s, 6H, –CH₃), 13 C-NMR:(DMSO-d₆, p.p.m.) δ: 197.98 (C=S), 159.15 (C=N), 129.32–142.86 (Ar–C), 128.39–129.90 (thiophene-C), 38.23 (SCH₂), 15.58, 21.24 (CH₃).