Crystal structure of 2-((1E)-{2-[bis­(2-methyl­benzyl­sulfan­yl)methyl­idene]hydrazin-1-yl­idene}meth­yl)-6-meth­oxy­phenol

Enis Nadia Md Yusof; Thahira Begum S A Ravoof; Mohamed Ibrahim Mohamed Tahir; Edward R T Tiekink

doi:10.1107/S2056989015004946

. 2015 Mar 18;71(Pt 4):o242–o243. doi: 10.1107/S2056989015004946

Crystal structure of 2-((1E)-{2-[bis(2-methylbenzylsulfanyl)methylidene]hydrazin-1-ylidene}methyl)-6-methoxyphenol

Enis Nadia Md Yusof ^a, Thahira Begum S A Ravoof ^a,^*, Mohamed Ibrahim Mohamed Tahir ^a, Edward R T Tiekink ^b

PMCID: PMC4438809 PMID: 26029435

Abstract

In the title compound, C₂₅H₂₆N₂O₂S₂, the central CN₂S₂ atoms are almost coplanar (r.m.s. deviation = 0.0058 Å). One phenyl ring clearly lies to one side of the central plane, while the other is oriented in the plane but splayed. Despite the different relative orientations, the phenyl rings form similar dihedral angles of 64.90 (3) and 70.06 (3)° with the central plane, and 63.28 (4)° with each other. The benzene ring is twisted with respect to the central plane, forming a dihedral angle of 13.17 (7)°. The S₂C=N, N—N and N—N=C bond lengths of 1.2919 (19), 1.4037 (17) and 1.2892 (19) Å, respectively, suggest limited conjugation over these atoms; the configuration about the N—N=C bond is E. An intramolecular O—H⋯N hydrogen bond is noted. In the crystal, phenyl–methoxy C—H⋯O and phenyl–phenyl C—H⋯π interactions lead to supramolecular double chains parallel to the b axis. These are connected into a layer via methyl–phenyl C—H⋯π interactions, and layers stack along the a axis, being connected by weak π–π interactions between phenyl rings [inter-centroid distance = 3.9915 (9) Å] so that a three-dimensional architecture ensues.

Keywords: crystal structure, S-substituted dithiocarbazates, hydrogen bonding, C—H⋯π interactions, π–π interactions

Related literature

For background to the coordination chemistry of dithiocarbazate derivatives, see: Tarafder et al. (2002 ▸); Ravoof et al. (2010 ▸, 2011 ▸); Omar et al. (2014 ▸). For related synthesis, see: Ali & Tarafder (1977 ▸); Tarafder et al. (2002 ▸); Manan et al. (2012 ▸). For a related structure but with the S atoms connected by an ethylene bridge, and with a terminal furan-2-yl ring, i.e. N-1,3-dithiolan-2-ylidene-N′-[(E)-furan-2-ylmethylidene]hydrazone, see: Liu et al. (2008 ▸). graphic file with name e-71-0o242-scheme1.jpg

Experimental

Crystal data

C₂₅H₂₆N₂O₂S₂
M _r = 450.60
Monoclinic,
a = 19.7865 (7) Å
b = 6.8600 (2) Å
c = 16.1805 (5) Å
β = 94.880 (3)°
V = 2188.31 (12) Å³
Z = 4
Cu Kα radiation
μ = 2.41 mm⁻¹
T = 100 K
0.25 × 0.11 × 0.08 mm

Data collection

Oxford Diffraction Xcaliber Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▸) T _min = 0.715, T _max = 1.000
40860 measured reflections
4248 independent reflections
3956 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.094
S = 1.04
4248 reflections
286 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.24 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) ml, I. DOI: 10.1107/S2056989015004946/hb7379sup1.cif

e-71-0o242-sup1.cif^{(1.4MB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015004946/hb7379Isup2.hkl

e-71-0o242-Isup2.hkl^{(233KB, hkl)}

Click here for additional data file.^{(8.8KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015004946/hb7379Isup3.cml

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989015004946/hb7379fig1.tif

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

Click here for additional data file.^{(1.8MB, tif)}

b . DOI: 10.1107/S2056989015004946/hb7379fig2.tif

A view of the unit-cell contents in projection down the b axis. The C—H⋯O, C—H⋯π and π—π interactions are shown as orange, purple and pink dashed lines, respectively.

CCDC reference: 1053188

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

Table 1. Hydrogen-bond geometry (, ).

Cg1 is the centroid of the C3C8 ring.

DHA	DH	HA	D A	DHA
O1H1ON2	0.84(2)	1.87(2)	2.6331(16)	151(2)
C5H5O2ⁱ	0.95	2.44	3.3868(18)	176
C7H7Cg1ⁱ	0.95	2.68	3.5046(15)	146
C9H9B Cg1ⁱⁱ	0.98	2.72	3.5482(17)	142

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

Acknowledgments

We thank the Department of Chemistry, Universiti Putra Malaysia for facilities. This research was funded by Universiti Putra Malaysia (UPM) and the Malaysian Government under the Geran UPM Scheme (RUGS No. IBT/2013/9419400), the Malaysian Fundamental Research Grant Scheme (FRGS No. 01–02-13–1344FR) and the ScienceFund under the Ministry of Science, Technology and Innovation (MOSTI 06–01-04-SF1810). ENMY wishes to thank UPM for the award of a Graduate Research Fellowship.

supplementary crystallographic information

S1. Experimental

The synthesis of S-2-methylbenzyldithiocarbazate (S2MBDTC) was accomplished as reported previously (Ravoof et al., 2011). The title compound was synthesized following an established literature procedure (Ravoof et al., 2011). S2MBDTC (2.12.g, 0.01 mol) was dissolved in hot acetonitrile (150 ml). This was added to an equimolar solution of 2-hydroxy-3-methoxybenzaldehyde (1.52 g, 0.01 mol) in ethanol (20 ml). The mixture was heated and stirred for 30 min and then allowed to stand for a few hours. The yellow crystals formed were filtered off and recrystallized from acetonitrile. Pale-yellow plates were obtained after 1 week by keeping the solution at room temperature.