Methyl 2-{2-[(E)-(2-hy­droxy-3-meth­oxy­benzyl­idene)amino]­ethyl­amino}­cyclo­pentene-1-carbodithio­ate

Saeid Menati; Ali Kakanejadi; Abbas Taeb; Giuseppe Bruno; Hadi Amiri Rudbari

doi:10.1107/S1600536811002972

. 2011 Jan 29;67(Pt 2):o535. doi: 10.1107/S1600536811002972

Methyl 2-{2-[(E)-(2-hydroxy-3-methoxybenzylidene)amino]ethylamino}cyclopentene-1-carbodithioate

Saeid Menati ^a,^*, Ali Kakanejadi ^b, Abbas Taeb ^a, Giuseppe Bruno ^c, Hadi Amiri Rudbari ^c

PMCID: PMC3051642 PMID: 21523183

Abstract

In the title Schiff base compound, C₁₇H₂₂N₂O₂S₂, which adopts an E configuration with respect to the imine C=N double bond, the C=N and N—C bond distances are 1.2789 (16) and 1.4546 (16) Å, respectively. In the molecule there are intramolecular O—H⋯N and N—H⋯S hydrogen bonds, and the CH=N—C substituent is almost coplanar with the benzene ring [C—N—C—C torsion angle = −178.80 (11)°]. The crystal packing is stabilized by intermolecular C—H⋯O and C—H⋯π interactions involving the aromatic ring.

Related literature

For properties and applications of Schiff base compounds, see: Sabater et al. (1999 ▶); Di Bella & Fragala (2002 ▶); Lecren et al. (2007 ▶); Güngör & Gürkan (2010 ▶). For related structures, see: Pereira et al. (2008 ▶); Kumar et al. (1995 ▶); Asadi et al. (2009 ▶).

Experimental

Crystal data

C₁₇H₂₂N₂O₂S₂
M _r = 350.49
Triclinic,
a = 7.7933 (2) Å
b = 10.3486 (2) Å
c = 11.9532 (3) Å
α = 108.038 (1)°
β = 93.349 (1)°
γ = 100.296 (1)°
V = 895.19 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 296 K
0.56 × 0.45 × 0.34 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.678, T _max = 0.746
34525 measured reflections
4761 independent reflections
4235 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.109
S = 1.05
4761 reflections
211 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811002972/su2251sup1.cif

e-67-0o535-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811002972/su2251Isup2.hkl

e-67-0o535-Isup2.hkl^{(233.3KB, hkl)}

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

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

Cg is the centroid of the C11–C16 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S2	0.86	2.32	3.0275 (11)	140
O2—H2⋯N2	0.82	1.85	2.5806 (14)	147
C9—H9B⋯O2ⁱ	0.97	2.51	3.1166 (16)	120
C1—H1C⋯Cgⁱⁱ	0.96	2.95	3.617 (2)	128

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

supplementary crystallographic information

Comment

Reflecting their usual relative ease of synthesis and excellent imine bonding properties, Schiff base compounds have been extensively investigated for more than a century. They have been employed in areas that include analytical and bioinorganic chemistry, non-linear optics, fluorescence studies, catalysis and materials chemistry (Sabater et al., 1999; Di Bella et al., 2002; Lecren et al., 2007). The development of simple methods to produce asymmetric products remains an area of considerable research activity (Güngör et al., 2010). In the other hand, it is well known that N and S atoms play a key role in the coordination of metals at the active sites of numerous metallobiomolecules. We are particularly interested in the synthesis and characterization of such asymmetric Schiff base compounds.

Three new asymmetric Schiff base compounds, (E)-methyl 2-(2-(2-hydroxy-3-methoxybenzylideneamino)ethylamino)cyclopent-1- enecarbodithioate (1), (E)-methyl 2-(2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)ethylamino) cyclopent-1-enecarbodithioate (2) and (E)-methyl 2-(2-(3-hydroxy-4-methoxybenzylideneamino)ethylamino) cyclopent-1- enecarbodithioate (3) have been prepared. Herein we report on the crystal structure of compound (1).

The molecular structure of compound (1) (Fig. 1) is similar to those of analogous derivatives (Pereira et al., 2008; Kumar et al., 1995; Asadi et al., 2009). The title molecule adopts an E configuration with respect to the imine C═N double bond, with a C11—C10—N2—C9 torsion angle of -178.80 (11)°. The C12—O2 bond distance of 1.3377 (15) Å suggests that it is the phenol-imine tautomer. The contraction of the C10═N2 bond [1.2789 (16) Å] is also in agreement with the phenol-imine tautomer. As for the methoxy group, the O1—C13 and O1—C17 bond distances are 1.365 (2) and 1.420 (2) Å, respectively, and the C13—O1—C17 bond angle is 116.50 (17) Å. The planarity of the molecule is stabilized by intramolecular O—H···N and N–H···S hydrogen bonds (Fig. 1 and Table 1). However, there are no intermolecular hydrogen bonds associated with the methoxy group.

The crystal packing in compound (1) is stabilized by C—H···O and C—H···π interactions; the later involving the aromatic ring (C11—C16) and the C1—H1C H-atom (Fig. 2 and Table 1).

Experimental

Methyl-2-{N-(2-aminoethane)}-amino-1-cyclopentenedithiocarboxylate (Hcden) was prepared by literature methods. The compounds (1), (2) and (3) were prepared by the addition of an equimolar amount of a methanolic solution of the appropriate benzaldehydr, 2-hydroxy-3-methoxybenzaldehyde, 3,5-di-tert-butyl-2-hydroxybenzaldehyde and 3-hydroxy-4-methoxybenzaldehyde, respectively, to a methanolic solution of Hcden. The products obtained were recrystallized from methanol/chloroform 1:1 (V:V).