3-(Adamantan-1-yl)-4-ethyl-1H-1,2,4-triazole-5(4H)-thione

Ali A El-Emam; Nasser R El-Brollosy; Hazem A Ghabbour; Ching Kheng Quah; Hoong-Kun Fun

doi:10.1107/S1600536812014407

. 2012 Apr 13;68(Pt 5):o1347. doi: 10.1107/S1600536812014407

3-(Adamantan-1-yl)-4-ethyl-1H-1,2,4-triazole-5(4H)-thione

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

PMCID: PMC3344481 PMID: 22590243

Abstract

In the title compound, C₁₄H₂₁N₃S, the 1,2,4-triazole ring is nearly planar, with a maximum deviation of 0.003 (4) Å. 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: Al-Omar et al. (2010 ▶); Al-Deeb et al. (2006 ▶); El-Emam et al. (2004 ▶); Kadi et al. (2007 ▶, 2010 ▶); Vernier et al. (1969 ▶). For the synthesis of the title compound, see: El-Emam & Ibrahim (1991 ▶). For related structures of adamantane derivatives, see: Almutairi et al. (2012 ▶); Al-Tamimi et al. (2010 ▶); Rouchal et al. (2010 ▶); Wang et al. (2011 ▶); Al-Abdullah et al. (2012 ▶). For standard bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₄H₂₁N₃S
M _r = 263.40
Monoclinic,
a = 13.8329 (7) Å
b = 7.3107 (4) Å
c = 17.5302 (12) Å
β = 128.157 (4)°
V = 1393.99 (16) Å³
Z = 4
Cu Kα radiation
μ = 1.94 mm⁻¹
T = 296 K
0.58 × 0.12 × 0.05 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.228, T _max = 0.906
8009 measured reflections
2448 independent reflections
1632 reflections with I > 2σ(I)
R _int = 0.093

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.167
S = 1.13
2448 reflections
168 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.26 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/S1600536812014407/is5108sup1.cif

e-68-o1347-sup1.cif^{(24.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014407/is5108Isup2.hkl

e-68-o1347-Isup2.hkl^{(120.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812014407/is5108Isup3.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
N2—H1N2⋯S1ⁱ	0.88 (4)	2.47 (4)	3.338 (4)	170 (4)

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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 derivatives were recently reported to exhibit marked antibacterial activity (Kadi et al., 2007, 2010). In an earlier publication, we reported the synthesis and potent anti-inflammatory and analgesic activities of a series of 5-(1-adamantyl)-4-substituted-4H-1,2,4-triazole-3-thiols and related derivatives including the title compound (El-Emam & Ibrahim, 1991).

In the title molecule (Fig. 1), the 1,2,4-triazole ring (N1–N3/C1/C2) is nearly planar with a maximum deviation of 0.003 (4)) Å at atom C1. Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to related structures (Almutairi et al., 2012; Al-Tamimi et al., 2010; Rouchal et al., 2010; Wang et al., 2011; Al-Abdullah et al., 2012).

In the crystal (Fig. 2), molecules are linked into inversion dimers by pairs of intermolecular N2—H2A···S1 hydrogen bonds (Table 1).

Experimental

A mixture of adamantane-1-carbohydrazide (1.94 g, 0.01 mol), ethyl isothiocyanate (0.87 g, 0.01 mol), in ethanol (10 ml) was heated under reflux with stirring for one hour and the solvent was distilled off in vacuo. Aqueous sodium hydroxide solution (10%, 15 ml) was added to the residue and the mixture was heated under reflux for 2 h, then filtered hot. On cooling, the mixture was acidified with hydrochloric acid and the precipitated crude product was filtered, washed with water, dried and crystallized from aqueous ethanol to yield 2.24 g (85%) of the title compound (C₁₄H₂₁N₃S) as colorless crystals. M.p.: 210-212 °C. ¹H NMR (CDCl₃, 500.13 MHz): δ 1.36 (t, 3H, CH₃CH₂, J = 7.0 Hz), 1.73 (s, 6H, Adamantane-H), 1.99 (m, 6H, Adamantane-H), 2.06 (s, 3H, Adamantane-H), 4.19 (q, 2H, CH₃CH₂), 11.60 (br. s, 1H, NH). ¹³C NMR (CDCl₃, 125.76 MHz): δ 13.99 (CH₃), 27.91, 35.48, 36.27, 39.75 (Adamantane-C), 41.17 (CH₂), 158.04 (C=N), 167.25 (C=S).