3-(Adamantan-1-yl)-4-ethyl-1-[(4-phenyl­piperazin-1-yl)meth­yl]-1H-1,2,4-triazole-5(4H)-thione

Ali A El-Emam; Ebtehal S Al-Abdullah; Hanaa M Al-Tuwaijri; Mohammed Said-Abdelbaky; Santiago García-Granda

doi:10.1107/S160053681202990X

. 2012 Jul 7;68(Pt 8):o2380–o2381. doi: 10.1107/S160053681202990X

3-(Adamantan-1-yl)-4-ethyl-1-[(4-phenylpiperazin-1-yl)methyl]-1H-1,2,4-triazole-5(4H)-thione

Ali A El-Emam ^a,^‡, Ebtehal S Al-Abdullah ^a, Hanaa M Al-Tuwaijri ^a, Mohammed Said-Abdelbaky ^b, Santiago García-Granda ^b,^*

PMCID: PMC3414308 PMID: 22904841

Abstract

The title compound, C₂₅H₃₅N₅S, has an approximately C-shaped conformation. The dihedral angle between the triazole and phenyl planes is 79.5 (2)°. The crystal structure consists of infinite chains parallel to the b axis, constructed by C—H⋯S hydrogen bonds between translation-related molecules. Adjacent chains are linked via weak C—H⋯C interactions between the adamantyl and phenyl groups.

Related literature

For the biological activity of adamantane derivatives and adamantyl-1,2,4-triazoles, see: Vernier et al. (1969 ▶); Al-Deeb et al. (2006 ▶); Al-Omar et al. (2010 ▶); El-Emam & Ibrahim (1991 ▶); El-Emam et al. (2004 ▶); Kadi et al. (2007 ▶, 2010 ▶). For related adamantyl-1,2,4-triazole structures, see: Al-Tamimi et al. (2010 ▶); Al-Abdullah et al. (2012 ▶); El-Emam et al. (2012 ▶); Lahsasni et al. (2012 ▶).

Experimental

Crystal data

C₂₅H₃₅N₅S
M _r = 437.65
Orthorhombic,
a = 27.382 (4) Å
b = 6.5083 (7) Å
c = 13.369 (2) Å
V = 2382.4 (5) Å³
Z = 4
Cu Kα radiation
μ = 1.36 mm⁻¹
T = 293 K
0.16 × 0.06 × 0.02 mm

Data collection

Oxford Diffraction Xcalibur Gemini R diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.919, T _max = 1.000
5844 measured reflections
3016 independent reflections
1828 reflections with I > 2σ(I)
R _int = 0.086

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.128
S = 1.00
3016 reflections
282 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ▶), 632 Friedel pairs
Flack parameter: 0.00 (4)

Data collection: CrysAlis CCD (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2010 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681202990X/fy2061sup1.cif

e-68-o2380-sup1.cif^{(25.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681202990X/fy2061Isup2.hkl

e-68-o2380-Isup2.hkl^{(148KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681202990X/fy2061Isup3.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
C15—H15A⋯S1ⁱ	0.97	2.90	3.836 (5)	162
C5—H5A⋯C20ⁱⁱ	0.97	2.80	3.750 (6)	167

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

Acknowledgments

The financial support of the Deanship of Scientific Research and the Research Center for Female Scientific and Medical Colleges, King Saud University, is greatly appreciated. The authors are grateful for financial support from the Spanish Ministerio de Economía y Competitividad (MAT2010-15094, MAT2006-01997, Factoría de Cristalización – Consolider Ingenio 2010, and FPI grant BES-2011-046948 to MSM-A.) and FEDER.

supplementary crystallographic information

Comment

Adamantane derivatives were early recognized for their diverse biological activities including antiviral activity against the influenza (Vernier et al., 1969) and HIV viruses (El-Emam et al., 2004). In addition, adamantane derivatives were reported to exhibit marked antibacterial (Kadi et al., 2007, 2010) and anti-inflammatory (El-Emam & Ibrahim, 1991) activities. In continuation to our interest in the chemical and pharmacological properties of adamantane derivatives, we synthesized the title compound (I) as a potential bioactive agent. The structure consists of infinite chains parallel to the b axis, constructed by translations of a single molecule. The molecules in the the same chain are connected through C—H···S interactions with a H···S distance of 2.90 Å. Moreover, chains are linked via the weak C5—H5B···C20 interaction with a bond distance of 2.80 Å. The plane of the 1,2,4-triazole ring includes the S,C(ethyl group), C (adamantyl group) and C15 substituent atoms with deviations from the L.S. plane (in Å) of 0.0582, -0.1062, 0.0568 and -0.0964, respectively. The phenyl ring plane includes atom N5 with a deviation of 0.0668 Å. The angle between these two planes is 79.5 (2)°.

Experimental

A mixture of 527 mg (2 mmol) of 3-(1-adamantyl)-4-ethyl-4H-1,2,4-triazole-5-thiol (El-Emam & Ibrahim, 1991), 1-phenylpiperazine (325 mg, 2 mmol) and 37% formaldehyde solution (1 ml), in ethanol (8 ml), was heated under reflux for 15 min when a clear solution was obtained. Stirring was continued for 12 h at room temperature and the mixture was allowed to stand overnight. Cold water (5 ml) was slowly added and the mixture was stirred for 20 min. The precipitated crude product was filtered, washed with water, dried, and crystallized from ethanol to yield 770 mg (88%) of the title compound (C₂₅H₃₅N₅S) as colorless needle crystals. M.P.: 139–141°C. Single crystals suitable for X-ray analysis were obtained by slow evaporation of CHCl₃:EtOH solution (1:1; 5 ml) at room temperature. ¹H NMR (CDCl₃, 500.13 MHz): δ 1.13 (t, 3H, CH₂CH₃, J = 7.0 Hz), 1.67–1.73 (m, 6H, Adamantane-H), 1.96 (s, 6H, Adamantane-H), 2.03 (s, 3H, Adamantane-H), 2.88 (s, 4H, Piperazine-H), 3.09 (s, 4H, Piperazine-H), 4.17 (q, 2H, CH₂CH₃, J = 7.0 Hz), 5.08 (s, 2H, CH₂), 6.46–6.83 (m, 3H, Ar—H), 7.15–7.17 (m, 2H, Ar—H). ¹³C NMR (CDCl₃, 125.76 MHz): δ 13.81 (CH₂CH₃), 27.95, 35.24, 36.31, 39.90 (Adamantane-C), 43.43 (CH₂CH₃), 49.40, 50.37 (Piperazine-C), 68.80 (CH₂), 116.32, 119.99, 129.12, 151.27 (Ar—C), 156.10 (Triazole C-5), 168.75 (C=S).