2-Chloro-N′-[4-(dimethyl­amino)­benzyl­idene]-N-[4-(3-methyl-3-phenyl­cyclo­but­yl)-1,3-thia­zol-2-yl]acetohydrazide

Ersin Inkaya; Muharrem Dinçer; Alaaddin Çukurovalı; Engin Yılmaz

doi:10.1107/S1600536810049962

. 2010 Dec 15;67(Pt 1):o131–o132. doi: 10.1107/S1600536810049962

2-Chloro-N′-[4-(dimethylamino)benzylidene]-N-[4-(3-methyl-3-phenylcyclobutyl)-1,3-thiazol-2-yl]acetohydrazide

Ersin Inkaya ^a,^*, Muharrem Dinçer ^a, Alaaddin Çukurovalı ^b, Engin Yılmaz ^c

PMCID: PMC3050246 PMID: 21522642

Abstract

The molecular conformation of the title compound, C₂₅H₂₇ClN₄OS, is stabilized by an intramolecular benzylidine C—H⋯N_thiazole hydrogen bond. The thiazole ring makes dihedral angles of 12.0 (3) and 20.4 (2)°, respectively, with the phenyl and benzene rings, while the phenyl and benzene rings make a dihedral angle of 22.6 (2)°. The crystal packing involves weak intermolecular thiazole C—H⋯O_carbonyl and methyl C—H⋯π hydrogen-bonding associations.

Related literature

For applications of related compounds, see: Brown et al. (1974 ▶); Dehmlow & Schmidt (1990 ▶); Foerster et al. (1979) ▶; Roger et al. (1977 ▶); Sawhney et al. (1978) ▶; Slip et al. (1974) ▶; Suzuki et al. (1979) ▶. For background to Schiff bases, see: Costamagna et al. (1992 ▶); Fita et al. (2005 ▶); Sridharan et al. (2004 ▶). For related structures, see: Dinçer et al. (2004 ▶); Demir et al. (2006 ▶); Özdemir et al. (2004 ▶); Soylu et al. (2005 ▶); Xu et al. (1994 ▶). For bond-length data, see: Allen (1984 ▶).

Experimental

Crystal data

C₂₅H₂₇ClN₄OS
M _r = 467.02
Monoclinic,
a = 9.0194 (5) Å
b = 26.7946 (11) Å
c = 13.1773 (7) Å
β = 132.054 (3)°
V = 2364.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 296 K
0.62 × 0.36 × 0.02 mm

Data collection

Stoe IPDS 2 CCD diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.533, T _max = 0.896
22742 measured reflections
4446 independent reflections
2250 reflections with I > 2σ(I)
R _int = 0.143

Refinement

R[F ² > 2σ(F ²)] = 0.070
wR(F ²) = 0.121
S = 1.01
4446 reflections
292 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810049962/zs2082sup1.cif

e-67-0o131-sup1.cif^{(23.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049962/zs2082Isup2.hkl

e-67-0o131-Isup2.hkl^{(213.4KB, hkl)}

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯N1	0.93	2.21	2.838 (5)	124
C13—H13⋯O1ⁱ	0.93	2.50	3.374 (5)	157
C16—H16A⋯Cg1ⁱⁱ	0.97	2.57	3.493	159

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

Acknowledgments

This study was supported financially by the Research Center of Ondokuz Mayıs University (Project No. F-461).

supplementary crystallographic information

Comment

3-Substituted cyclobutane carboxylic acids exhibit anti-inflammatory and anti-depressant activity (Roger et al.,1977), as well as having liquid crystal properties (Dehmlow & Schmidt, 1990). Also, various thiazole derivatives have been shown to possess herbicidal (Foerster, et al., 1979), anti-inflammatory (Sawhney et al., 1978; Brown et al., 1974), anti-microbial (Suzuki et al.,1979), and anti-parasitic properties (Slip et al., 1974). Schiff bases are important in the development of coordination chemistry and Schiff base ligands are of interest mainly because of the existence of typical hydrogen bonds and tautomerism between the phenol–imine and keto–amine forms (Costamagna et al., 1992; Sridharan et al., 2004; Fita et al., 2005). The synthesis and structure of the title compound, N-(4-dimethylaminobenzylidene)-N- [4-(3-methyl-3-phenyl-cyclobutyl)-thiazol-2-yl]-chloroacetic acid hydrazide, C₂₅H₂₇N₄OClS (I) is reported here.

In the structure of (I) (Fig. 1) the phenyl and thiazole rings are cis-related with respect to the cyclobutane ring. The cyclobutane ring is puckered, with a dihedral angle of 22.99 (47)° between the two three-membered halves of the ring, which is more puckered than other similar examples from the literature, e.g. 11.55 (3)°, (Özdemir et al., 2004) and 19.8 (3)° (Dinçer et al., 2004). The dihedral angle between plane A (C1—C6), the thiazole plane B (N1/C14/S1/C13/C12) and the phenyl plane C (C18—C21) are 11.95 (25)° (A/B), 22.61 (23)° (A/C) and 20.36 (23)° (B/C), respectively. In the thiazole ring, the S1—C14 and S1—C13 bond lengths are 1.743 (4) Å and 1.707 (4) Å which are shorter than the accepted value for an S—Csp² single bond (1.76 Å; Allen, 1984) and is the result the conjugation of the electrons of atom S1 with atoms C14 and C13. The C—Cl and C═O bond distances are 1.779 (3) Å and 1.217 (4) Å, respectively, and these values are significantly shorter than those in the literature [1.807 (12) and 1.187 (16) Å, respectively (Demir et al., 2006]. The C17═N3 bond length [1.276 (4) Å] compares with a literature value of 1.285 (7) Å (Xu et al., 1994). In the thiazole ring the C12—N1 and C14═N1 bond lengths [1.389 (5) and 1.292 (4) Å, respectively] compare with literature values of 1.394 (4) and 1.339 (4)Å, respectively (Soylu et al., 2005).

The conformation of the azide substituent ring systems of the title compound is stabilized by an intramolecular benzylidine C17—H···N1_thiazole hydrogen bond (Fig. 1, Table 1) and crystal packing involves weak intermolecular thiazole C13—H···O1_carbonyl and methyl C16—H···π (phenyl ring C1–C6) hydrogen-bonding associations (Fig. 2).

Experimental

A solution of 1 mmol of chloroacetyl chloride in 10 ml of 1,4-dioxane was added to a mixture of 0.3905 g (1 mmol) of dimethyl-(4-{[4-(3-methyl-3-phenyl-cyclobutyl)-thiazol-2-yl]-hydrazonomethyl} -phenylamine and 1 mmol of triethylamine in 20 ml of 1,4-dioxane, at room temperature with continuous stirring. The course of the reaction was monitored by IR spectroscopy. The target product was precipitated with the slow addition of water, filtered, washed with copious cold ethanol and dried in air. The shiny crystals suitable for X-ray analysis was obtained by slow evaporation from an alcoholic solution. Yield: 83%, m.p. 420 K (EtOH). IR (KBr, ν cm^-1): 2974–2813 (aliphatic), 1703 (C=O), 1612 (C=N thiazole), 728 (–CH₂—Cl),634 (C—S). ¹H NMR (CDCl₃, TMS, δ, p.p.m.): 1.57 (s, 3H, –CH₃, on cyclobutane), 2.50–2.65 (m, 4H, –CH₂– on cyclobutane), 3.05 (s, 6H, –CH₃ on aniline),3.77 (quint, j = 8.78 Hz, 1H, >CH– on cyclobutane),4.80 (s, 2H, –CH₂—Cl),6.66 (d, j = 8.78 Hz, 2H, aromatic), 6.82 (s, 1H, =CH—S on thiazole), 7.14–7.21 (m, 3H, aromatics), 7.28 (t, j = 6.95 Hz, 2H, aromatic), 7.44 (d, j = 8.78 Hz, 2H, aromatic), 8.78 (s, 1H, –N═CH– azomethine). ¹³C NMR (CDCl₃, TMS, δ, p.p.m.): 167.07, 156.56, 155.42, 152.71, 152.38, 129.88, 128.46, 125.50, 125.00, 120.90, 111.89, 111.30, 44.03, 41.21, 40.35, 38.95, 31.01, 30.10.