3-(1-Adamant­yl)-4-amino-1-(2-benzoyl-1-phenyl­eth­yl)-1H-1,2,4-triazol-5(4H)-thione

Siham Lahsasni; Ali A El-Emam; Nasser R El-Brollosy; Ching Kheng Quah; Hoong-Kun Fun

doi:10.1107/S1600536812015929

. 2012 Apr 18;68(Pt 5):o1439–o1440. doi: 10.1107/S1600536812015929

3-(1-Adamantyl)-4-amino-1-(2-benzoyl-1-phenylethyl)-1H-1,2,4-triazol-5(4H)-thione

Siham Lahsasni ^a, Ali A El-Emam ^b, Nasser R El-Brollosy ^b, Ching Kheng Quah ^c,^‡, Hoong-Kun Fun ^c,^*,^§

PMCID: PMC3344558 PMID: 22590320

Abstract

In the title compound, C₂₇H₃₀N₄OS, the 3-(adamantan-1-yl)-4-amino-1H-1,2,4-triazole-5(4H)-thione unit and the O atom are each disordered over two sets of sites with refined site-occupancies of 0.7630 (13) and 0.2370 (13). The 1,2,4-triazole ring of the major component forms dihedral angles of 62.61 (17) and 61.93 (16)° with the benzene rings, while that of the minor component makes corresponding angles of 86.3 (4) and 79.1 (4)°. The dihedral angle between the benzene rings is 39.21 (16)°. The molecular structure is stabilized by an intramolecular C—H⋯N hydrogen bond, which generates an S(6) ring motif. In the crystal, molecules are linked into inversion dimers by pairs of N—H⋯S hydrogen bonds.

Related literature

For the biological activity of adamantane derivatives, see: Vernier et al. (1969 ▶); Kadi et al. (2007 ▶, 2010 ▶); Al-Abdullah et al. (2007 ▶); El-Emam et al. (2004 ▶). For related adamantyl-1,2,4-triazole structures, see: Al-Abdullah et al. (2012 ▶); Almutairi et al. (2012 ▶); Al-Tamimi et al. (2010 ▶). For related amino-1,2,4-triazole structures, see: Song et al. (2011 ▶); Gao et al. (2011 ▶); Wang et al. (2011 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₇H₃₀N₄OS
M _r = 458.61
Monoclinic,
a = 11.9409 (3) Å
b = 9.5478 (3) Å
c = 22.0034 (6) Å
β = 103.610 (2)°
V = 2438.15 (12) Å³
Z = 4
Cu Kα radiation
μ = 1.38 mm⁻¹
T = 296 K
0.98 × 0.66 × 0.33 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.345, T _max = 0.662
18569 measured reflections
4512 independent reflections
3341 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.140
S = 1.04
4512 reflections
371 parameters
30 restraints
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 datablock(s) global, I. DOI: 10.1107/S1600536812015929/is5114sup1.cif

e-68-o1439-sup1.cif^{(44.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812015929/is5114Isup2.hkl

e-68-o1439-Isup2.hkl^{(221.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812015929/is5114Isup3.cml

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
N4—H1N4⋯S1ⁱ	0.90	2.60	3.475 (3)	166
C4—H4B⋯N4	0.97	2.53	3.177 (4)	124

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

The financial support of the Deanship of Scientific Research and the Research Center of the College of Pharmacy, King Saud University, is greatly appreciated. HKF and CKQ thank Universiti Sains Malaysia (USM) for the Research University Grant (No. 1001/PFIZIK/811160).

supplementary crystallographic information

Comment

Derivatives of adamantane have long been known for their diverse biological activities including antiviral activity against the influenza (Vernier et al., 1969) and HIV viruses (El-Emam et al., 2004). Moreover, adamantane derivative were recently reported to exhibit marked antibacterial activity (Kadi et al., 2007, 2010). In continuation to our interest in the reactions of amino-1,2,4-triazoles (Al-Abdullah et al., 2007), we report herein the synthesis and structure of the title compound (I) as potential chemotherapeutic agent.

In the title molecule, Fig. 1, the 3-(adamantan-1-yl)-4-amino-1H-1,2,4-triazole-5(4H)-thione moiety and an oxygen atom are disordered over two positions with refined site-occupancies of 0.763 (1):0.237 (1). The mean plane of major component of 1,2,4-triazole ring (N1-N3/C1/C2, r.m.s deviation = 0.003 Å) forms dihedral angles of 62.61 (17) and 61.93 (16)° with the two benzene rings (C16–C21 and C22–C27). The corresponding angles for minor component of 1,2,4-triazole ring (r.m.s deviation = 0.010 Å) are 86.3 (4) and 79.1 (4)°. The dihedral angle between the two benzene rings is 39.21 (16)°. Bond lengths (Allen et al., 1987) and angles are within normal ranges. The molecular structure is stabilized by an intramolecular C4—H4B···N4 hydrogen bond (Table 1), which generates an S(6) ring motif (Fig. 2; Bernstein et al., 1995).

In the crystal (Fig. 3), molecules are linked into inversion dimers by pairs of N4—H1N4···S1 hydrogen bonds (Table 1).

Experimental

A mixture of 3-(1-adamantyl)-4-amino-4H-1,2,4-triazole-5-thiol (2.5 g, 0.01 mol) and (E)-1-(4-phenyl)-3-phenylprop-2-en-1-one (2.08 g, 0.01 mol), in ethanol (15 ml), was heated under reflux for 10 h and the solvent was then distilled off in vacuo. The resulted residue was eluted from silica gel column using hexane:ethyl acetate (4:1) to yield 1.01 g (22%) of the title compound (I) as pale yellow powder. M.p. 191-193°C. Crystals of (I) suitable for single crystal X-ray analysis were grown by slow evaporation of a solution in chloroform-ethanol (1:1) at room temperature. ¹H NMR (CDCl₃, 500.13 MHz): δ 1.66 (s, 6H, Adamantane-H), 1.95 (s, 9H, Adamantane-H), 3.45-3.49 (m, 1H^a, CH₂CO), 4.23-4.29 (m, 1H^b, CH₂CO), 4.51 (s, 2H, NH₂), 6.48-6.51 (m, 1H, CH), 7.18-7.27 (m, 3H, Ar-H), 7.36-7.48 (m, 5H, Ar-H), 7.88-7.90 (m, 2H, Ar-H). ¹³C NMR (CDCl₃, 125.76 MHz): δ 27.84, 35.0, 36.42, 38.41 (Adamantane-C), 42.75 (CH), 58.09 (CH₂), 127.54, 128.14, 128.24, 128.60, 128.71, 133.30, 136.66, 138.71 (Ar-C), 156.25 (Triazole C-3), 167.55 (C=S), 196.09 (C=O).