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

Hoong-Kun Fun; Samuel Robinson Jebas; K V Sujith; P S Patil; B Kalluraya; S M Dharmaprakash

doi:10.1107/S1600536808012713

. 2008 May 7;64(Pt 6):o1001–o1002. doi: 10.1107/S1600536808012713

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

Hoong-Kun Fun ^a,^*, Samuel Robinson Jebas ^a,^‡, K V Sujith ^b, P S Patil ^c, B Kalluraya ^b, S M Dharmaprakash ^c

PMCID: PMC2961489 PMID: 21202529

Abstract

In the title compound, C₃₄H₃₄BrN₅S, the two phenyl rings of the diphenylaminomethyl group are inclined at an angle of 73.86 (8)° and they form dihedral angles of 74.04 (8) and 48.74 (8)° with the triazole ring. Intramolecular C—H⋯S hydrogen bonds generate S(6) and S(5) ring motifs. The crystal structure is stabilized by weak C—H⋯π interactions.

Related literature

For related literature, see: Dave et al. (2007 ▶); Kalluraya et al. (2003 ▶, 2004 ▶, 2007 ▶); Kane et al. (1990 ▶). For literature on Mannich bases, see: Kalluraya et al. (2001 ▶). For bond-length data, see: Allen et al. (1987 ▶). For related literature on hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₃₄H₃₄BrN₅S
M _r = 624.63
Monoclinic,
a = 10.9672 (1) Å
b = 9.7833 (1) Å
c = 28.6210 (3) Å
β = 105.966 (1)°
V = 2952.44 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.50 mm⁻¹
T = 100.0 (1) K
0.35 × 0.31 × 0.27 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.623, T _max = 0.684
55283 measured reflections
13248 independent reflections
7914 reflections with I > 2σ(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.098
S = 1.01
13248 reflections
372 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); 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, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808012713/ci2592sup1.cif

e-64-o1001-sup1.cif^{(28KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808012713/ci2592Isup2.hkl

e-64-o1001-Isup2.hkl^{(634.6KB, 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
C3—H3A⋯S1	0.93	2.52	3.217 (2)	132
C22—H22B⋯S1	0.97	2.80	3.232 (2)	108
C6—H6A⋯Cg1ⁱ	0.93	2.81	3.717 (2)	165
C21—H21C⋯Cg2ⁱⁱ	0.96	2.89	3.829 (2)	168

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 and Cg2 are the centroids of the C11–C16 and C23–C28 rings, respectively.

Acknowledgments

HKF and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

Nitrogen-containing heterocyclic molecules constitute the largest portion of chemical entities, which are part of many natural products, fine chemicals, and biologically active pharmaceuticals vital for enhancing the quality of life (Kalluraya et al. 2003, 2007; Kane et al., 1990). Mannich bases are a class of heterocycles, which have attracted significant interest in medicinal chemistry (Kalluraya et al., 2004). Among the Mannich bases, 1,2,4-triazole derivatives have attracted considerable attention because of their wide variety of biological activities, such as antineoplastic, analgesic and antibiotic activity (Dave et al., 2007). Mannich bases are obtained by condensing an amine, formaldehyde and a compound containing active hydrogen atom (Kalluraya et al., 2001). It is interesting to note that the reaction is highly regioselective and furnishes only the N-Mannich base and none of the S-Mannich derivatives, though the intermediate Schiff bases can exist in the thiol-thione tautomeric equilibrium. In view of these impressive array of properties exhibited by Mannich bases, the crystal structure of the title compound is reported here.

Bond lengths and angles in the title compound have normal values (Allen et al., 1987). The triazole ring is planar with a maximium deviation of 0.010 (2) Å for atom C1. The planes through the C4—C9, C11—C16, C23—C28 and C29—C34 rings form dihedral angles of 25.10 (8), 81.35 (8), 74.04 (8) and 48.74 (8)°, respectively, with the the triazole ring. Weak C—H···S hydrogen bonds generating S(6) and S(5) ring motifs (Bernstein et al.,(1995) are observed in the molecular structure.

The crystal packing is stabilized by weak C—H···π interactions involving the C11–C16 (centroid Cg1) and C23–C28 (centroid Cg2) rings (Table 1).

Experimental

The title compound, a Mannich base, was obtained by the aminomethylation of a Schiff base, 4-{[(4-bromophenyl)methylene]amino}-5-[1-(4-isobutylphenyl)ethyl]-3-mercapto- 1,2,4-triazole which was in turn obtained by refluxing 4-amino-3-mercapto-5- [1-(4-isobutylphenyl)ethyl]-1,2,4-triazole (0.01 mol) and 4-bromo benzaldehyde (0.01 mol) in ethanol (30 ml) by adding 2 drops of concentrated sulfuric acid for 3 h. A mixture of the obtained Schiff base (0.01 mol), formaldehyde (40%, 1 ml) and diphenyl amine (0.01 mol) in ethanol (50 ml) was stirred at room temperature for 16 h. The solid product was collected by filtration, washed with ethanol and dried. It was then recrystallized from ethanol. Crystals suitable for X-ray analysis were obtained from an acetone-N,N-dimethylformamide (DMF) (1:3) solution by slow evaporation (yield 68%; m.p. 381–382 K). Analysis (%) for C₃₄H₃₄N₅BrS found (calculated): C 65.23 (65.38), H 5.33 (5.44), N 11.21 (11.17).