4-[(4-Fluoro­benzyl­idene)amino]-3-[1-(4-isobutyl­phen­yl)eth­yl]-1H-1,2,4-triazole-5(4H)-thione

Hoong-Kun Fun; Wan-Sin Loh; A C Vinayaka; B Kalluraya

doi:10.1107/S160053680903030X

. 2009 Aug 8;65(Pt 9):o2079–o2080. doi: 10.1107/S160053680903030X

4-[(4-Fluorobenzylidene)amino]-3-[1-(4-isobutylphenyl)ethyl]-1H-1,2,4-triazole-5(4H)-thione

Hoong-Kun Fun ^a,^*,^‡, Wan-Sin Loh ^a, A C Vinayaka ^b, B Kalluraya ^b

PMCID: PMC2969932 PMID: 21577498

Abstract

In the title compound, C₂₁H₂₃FN₄S, the benzene rings of the isobutylphenyl and fluorobenzene units form dihedral angles of 75.89 (7) and 13.26 (7)°, respectively, with the triazole ring. An intramolecular C—H⋯S hydrogen-bonding contact generates an S(6) ring motif. In the crystal packing, pairs of N—H⋯S hydrogen bonds link neighbouring molecules into inversion dimers, forming R ₂ ²(8) ring motifs. The crystal structure is further stabilized by C—H⋯π interactions.

Related literature

For pharmacological activity of triazoles, see: Göknur et al. (2005 ▶). For the anti-tumor activity of triazole derivatives, see: Demirbas et al. (2002 ▶, 2004 ▶). For the synthesis of related heterocyclic compounds, see: Fun et al. (2008 ▶, 2009a ▶). For a related structure, see: Fun et al. (2009b ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₁H₂₃FN₄S
M _r = 382.49
Triclinic,
a = 5.7883 (1) Å
b = 9.9001 (1) Å
c = 18.4972 (3) Å
α = 98.132 (1)°
β = 97.087 (1)°
γ = 105.997 (1)°
V = 993.90 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 100 K
0.46 × 0.20 × 0.07 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.919, T _max = 0.987
31031 measured reflections
7460 independent reflections
5798 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.135
S = 1.06
7460 reflections
336 parameters
All H-atom parameters refined
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903030X/tk2518sup1.cif

e-65-o2079-sup1.cif^{(22.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680903030X/tk2518Isup2.hkl

e-65-o2079-Isup2.hkl^{(365KB, 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
N3—H1N3⋯S1ⁱ	0.85 (2)	2.43 (2)	3.2763 (12)	172.3 (18)
C7—H7A⋯S1	0.96 (2)	2.50 (2)	3.2415 (13)	133.2 (16)
C4—H4A⋯Cg1ⁱⁱ	1.01 (2)	2.85 (2)	3.6276 (16)	133.8 (17)

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 is the centroid of the C11–C16 ring.

Acknowledgments

HKF and WSL thank Universiti Sains Malaysia (USM) for a Research University Golden Goose Grant (1001/PFIZIK/811012). WSL thanks USM for a student assistantship.

supplementary crystallographic information

Comment

1,2,4-Triazoles and their derivatives represent a rapidly developing field in modern heterocyclic chemistry. Similarly, ibuprofen belongs to the class of Non-Steroidal Anti-Inflammatory Drugs (NSAIDs) with diverse pharmacological activities. The analgesic, anti-asthematic, diuretic, anti-hypertensive and anti-inflammatory properties associated with these drugs have made them important chemotherapeutic agents (Göknur et al., 2005). Our earlier studies involved the synthesis of heterocyclic compounds incorporating ibuprofen and 1,2,4-triazole fragments in the structures (Fun et al., 2008, 2009a). Schiff base derivatives of 1,2,4-triazole are known to possess anti-tumor activity (Demirbas et al., 2004). Similarly, some Schiff base derivatives of acetic acid hydrazides containing 1,2,4-triazol-5-one ring have displayed anti-tumoral activity only against breast cancer, while 2-phenyl ethylidenamino and 2-phenyl ethylamino derivatives of 4-amino-1,2,4-triazol-5-ones have been found to be effective towards non-small cell lung cancer, cranial neural crest cancer, and breast cancer (Demirbas et al., 2002). In this connection and in continuation of our interest in the synthesis of chemically and biologically important heterocycles, we now report a substituted 1,2,4-triazole Schiff base carrying the ibuprofen moiety, (I).

In (I), Fig. 1, the triazole ring (C8/C9/N2–N4) is approximately planar with a maximum deviation of 0.009 (1)° at atom N2. The dihedral angles formed by the triazole ring with C1–C6 and C11–C16 benzene rings are 13.26 (7) and 75.89 (7)°, respectively. Bond lengths and angles are comparable to a closely related structure (Fun et. al., 2009b). An intramolecular C7—H7A···S1 hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995), Fig. 1.

In the crystal packing (Fig. 2), pairs of N3—H1N3···S1 hydrogen bonds link molecules into dimers forming R₂²(8) ring motifs; these stack along the a axis. The crystal structure is further stabilized by C—H···π interactions (Table 1).

Experimental

Compound (I) was obtained by refluxing 4-amino-5-[1-(4-isobutylphenyl)ethyl]-4H-1,2,4-triazole-3-thiol (0.01 mol) and 4-fluorobenzaldehyde (0.01 mol) in ethanol (50 ml) with 3 drops of concentrated sulfuric acid for 6 h. The solid product obtained was collected by filtration, washed with ethanol and dried. Crystals were obtained from the slow evaporation of an ethanol solution of (I).