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

Maha S Almutairi; Mona M Al-Shehri; Ali A El-Emam; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536812005065

. 2012 Feb 10;68(Pt 3):o656. doi: 10.1107/S1600536812005065

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

Maha S Almutairi ^a, Mona M Al-Shehri ^a, Ali A El-Emam ^a,^‡, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3295448 PMID: 22412559

Abstract

The title molecule, C₁₅H₂₁N₃S, exists as the thione tautomer in the solid state. The 1,2,4-triazole ring is almost planar (r.m.s. deviation = 0.004 Å) and the prop-2-en-1-yl chain is close to being perpendicular to this plane [C—N—C—C torsion angle = 77.1 (5)°]. In the crystal, centrosymmetric dimeric aggregates are formed by pairs of N—H⋯S hydrogen bonds as parts of eight-membered (⋯HNCS)₂ synthons. These are connected into layers parallel to (101) via C—H⋯π interactions, where the π-system is the triazole ring. The investigated sample was a nonmerohedral twin; the refined domain ratio was 0.655 (4):0.345 (4).

Related literature

For the biological activity of adamantyl derivatives, see: Vernier et al. (1969 ▶); El-Emam et al. (2004 ▶). Kadi et al. (2007 ▶, 2010 ▶). For the biological activity of adamantyl-1,2,4-triazole derivatives, see: Al-Deeb et al. (2006 ▶). For the separation of diffraction data into twin domains, see: Spek (2009 ▶).

Experimental

Crystal data

C₁₅H₂₁N₃S
M _r = 275.41
Monoclinic,
a = 13.5833 (17) Å
b = 8.6483 (6) Å
c = 13.6973 (14) Å
β = 115.938 (14)°
V = 1447.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 100 K
0.35 × 0.15 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.929, T _max = 0.979
10998 measured reflections
3324 independent reflections
2875 reflections with I > 2σ(I)
R _int = 0.077

Refinement

R[F ² > 2σ(F ²)] = 0.081
wR(F ²) = 0.230
S = 1.17
3324 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812005065/hb6626sup1.cif

e-68-0o656-sup1.cif^{(19.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812005065/hb6626Isup2.hkl

e-68-0o656-Isup2.hkl^{(159.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812005065/hb6626Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

Cg1 is the centroid of the C1/C2/N1/N2/N3 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯S1ⁱ	0.88	2.43	3.296 (3)	170
C5—H5⋯Cg1ⁱⁱ	1.00	2.60	3.529 (6)	155
C13—H13A⋯Cg1ⁱⁱⁱ	0.99	2.81	3.351 (5)	115

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

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. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research Scheme (grant No. UM.C/HIR/MOHE/SC/12).

supplementary crystallographic information

Comment

Derivatives of adamantane have long been known for their diverse biological activities including anti-viral 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 anti-bacterial activity (Kadi et al., 2007, 2010). In an earlier publication, we reported the synthesis and potent anti-microbial and anti-inflammatory activities for a series of 5-(1-adamantyl)-4-substituted-4H-1,2,4-triazole-3-thiols and related derivatives, including the title compound, (I) (Al-Deeb et al., 2006). Herein, the crystal and molecular structure is described which was performed to determine the tautomeric form of (I).

The key result of the structure determination of (I) is the confirmation of the thione form of the molecule, Fig. 1. The 1,2,4-triazole ring is planar [r.m.s. deviation = 0.004 Å] and the S1 atom lies 0.060 (1) Å out of this plane. The C13 atom lies even further out of the plane, i.e. by 0.155 (4) Å in the opposite direction to the S1 atom. The prop-2-en-1-yl chain is almost perpendicular to the plane through the five-membered ring as seen in the value of the C1—N1—C13—C14 torsion angle of 77.1 (5)°. The terminal ethene bond is directed toward the adamantyl group.

In the crystal packing, centrosymmetric dimeric aggregates are formed by N—H···S hydrogen bonds via eight-membered {···HNCS}₂ synthons. These are connected into a two-dimensional array parallel to (101) via C—H···π interactions, where the π-system is the triazole ring, Fig. 2 and Table 1. Layers stack without specific intermolecular interactions between them, Fig. 3.

Experimental

A mixture of adamantane-1-carbohydrazide (1.94 g, 0.01 mol) and allyl isothiocyanate (0.99 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 (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 2.18 g (79%) of (I) as colourless prisms. m.p. 468–470 K. ¹H NMR (CDCl₃): δ 1.75–1.83 (m, 6H, adamantane-H), 1.94 (s, 3H, adamantane-H), 2.05 (s, 6H, adamantane-H), 4.91 (s, 2H, CH₂), 5.03 (d, 1H, ═CHa, J = 17.0 Hz), 5.30 (d, 1H, ═CHb, J = 10.5 Hz), 5.90–5.96 (m, 1H, –CH═), 11.78 (br s, 1H, NH). ¹³C NMR: δ 27.88, 35.52, 36.27, 38.58 (adamantane-C), 47.66 (CH₂), 117.92 (═CH₂), 131.03 (–CH═), 158.34 (C═N), 168.61 (C═S).