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

Fatmah A M Al-Omary; Hazem A Ghabbour; Ali A El-Emam; C S Chidan Kumar; Hoong-Kun Fun

doi:10.1107/S1600536814013257

. 2014 Jun 14;70(Pt 7):o766–o767. doi: 10.1107/S1600536814013257

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

Fatmah A M Al-Omary ^a, Hazem A Ghabbour ^a, Ali A El-Emam ^a,^b,^*, C S Chidan Kumar ^c,^‡, Hoong-Kun Fun ^a,^c,^*,^§

PMCID: PMC4120616 PMID: 25161557

Abstract

The title compound, C₁₉H₂₃N₃S, is a functionalized triazoline-3-thione derivative. The benzyl ring is almost normal to the planar 1,2,4-triazole ring (r.m.s. deviation = 0.007 Å) with a dihedral angle of 86.90 (7)°. In the crystal, molecules are linked by pairs of N—H⋯S hydrogen bonds, forming inversion dimers that enclose R ₂ ²(8) loops. The crystal packing is further stabilized by weak C—H⋯π interactions that link adjacent dimeric units into supramolecular chains extending along the a-axis direction.

Related literature

For the biological activity of adamantane derivatives, see: Lorenzo et al. (2008 ▶); Al-Deeb et al. (2006 ▶); Wang et al. (2013 ▶); El-Emam et al. (2004 ▶); Kadi et al. (2010 ▶); Balzarini et al. (2009 ▶); Protopopova et al. (2005 ▶); Vernier et al. (1969 ▶). For related adamantyl-1,2,4-triazole structures, see: El-Emam et al. (2012 ▶), Al-Tamimi et al. (2013 ▶). For the synthesis of the title compound, see El-Emam & Ibrahim (1991 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). graphic file with name e-70-0o766-scheme1.jpg

Experimental

Crystal data

C₁₉H₂₃N₃S
M _r = 325.46
Triclinic,
a = 7.6407 (4) Å
b = 10.5150 (5) Å
c = 12.3434 (5) Å
α = 67.1806 (13)°
β = 72.9688 (13)°
γ = 70.0695 (14)°
V = 844.42 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 293 K
0.60 × 0.48 × 0.34 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.891, T _max = 0.937
43581 measured reflections
5166 independent reflections
4651 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.127
S = 1.08
5166 reflections
212 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814013257/sj5408sup1.cif

e-70-0o766-sup1.cif^{(26.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814013257/sj5408Isup2.hkl

e-70-0o766-Isup2.hkl^{(253KB, hkl)}

Click here for additional data file.^{(6.8KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814013257/sj5408Isup3.cml

CCDC reference: 1007119

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the N1–N3/C8/C9 triazole ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯S1ⁱ	0.85 (2)	2.44 (2)	3.2753 (11)	169.1 (18)
C19—H19B⋯Cg1ⁱⁱ	0.97	2.85	3.7885 (17)	141

Open in a new tab

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. CSCK thanks Universiti Sains Malaysia for a postdoctoral research fellowship.

supplementary crystallographic information

S1. Comment

Adamantane derivatives have long been known for their diverse biological activities (Lorenzo et al., 2008; Al-Deeb et al., 2006; Wang et al., 2013). These also include antiviral activity against influenza (Vernier et al., 1969) and HIV viruses (El-Emam et al., 2004; Balzarini et al., 2009). In addition, adamantane derivative were recently reported to exhibit marked antibacterial activity (Kadi et al., 2010; Protopopova et al., 2005). In an earlier publication, we reported the synthesis and potent anti-inflammatory 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 compound (Fig. 1), the 1,2,4-triazole (N1—N3/C8/C9) ring is nearly planar with a maximum deviation of -0.007 (1) Å at atom N2. The central 1,2,4-triazole ring forms dihedral angles of 86.90 (7)° and 69 (4)° with the adjacent phenyl (C1–C6) and adamantyl (C10–C19) substituents attached at the 4- and 5-positions, respectively. The attached phenyl ring is almost perpendicular to the plane of the triazole which is evident from the C9–N1–C7–C6 torsion angle of -95.63 (12)°. In the crystal packing (Fig. 2), centrosymmetric dimeric aggregates are formed by pairs of N2—H1N2···S1 hydrogen bonds resulting in an R₂²(8) ring motif (Bernstein et al., 1995). These are connected into supramolecular chains extending along the a axis direction via weak intermolecular C–H···π(triazole) interactions (Table 1).

S2. Experimental

A mixture of adamantane-1-carbohydrazide (1.94 g, 0.01 mol), benzyl isothiocyanate (1.49 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 2.93 g (90%) of the title compound (C₁₉H₂₃N₃S) as colorless crystals. M·P.: 241–243 °C.

¹H NMR (CDCl₃, 700.17 MHz): δ 1.64–1.69 (m, 6H, Adamantane-H), 1.90 (s, 6H, Adamantane-H), 2.20 (s, 3H, Adamantane-H), 5.53 (s, 2H, CH₂), 7.04–7.63 (s, 5H, Ar—H), 11.55 (br. s, 1H, NH). ¹³C NMR (CDCl₃, 176.08 MHz): δ 28.51, 35.66, 36.86, 39.08 (Adamantane-C), 63.56 (CH₂), 121.25, 123.0, 124.27, 130.54 (Ar—C), 154.06 (C=N), 164.41 (C=S).