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

Ali A El-Emam; Mohamed A Al-Omar; Abdul-Malek S Al-Tamimi; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536812021393

. 2012 May 19;68(Pt 6):o1772–o1773. doi: 10.1107/S1600536812021393

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

Ali A El-Emam ^a,^‡, Mohamed A Al-Omar ^a, Abdul-Malek S Al-Tamimi ^a, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3379353 PMID: 22719551

Abstract

The asymmetric unit of the title dichloromethane hemisolvate, C₂₄H₃₃N₅S·0.5CH₂Cl₂, comprises an adamantanyl/triazole derivative and half a CH₂Cl₂ molecule of crystallization; the latter is disordered about a twofold axis of symmetry. The piperazine ring has a chair conformation and the two N-bound substituents occupy equatorial positions. The piperazine residue is almost normal to the triazole ring [N—N—C—N torsion angle = −79.9 (3)°] so that to a first approximation, the molecule has an L-shape. Linear supramolecular chains parallel to [001] are formed via C—H⋯S interactions. Two such chains are linked into a double chain via C—H⋯Cl interactions involving the disordered CH₂Cl₂ molecules of solvation.

Related literature

For the diverse biological activities of adamantane derivatives, see: Al-Deeb et al. (2006 ▶); Al-Omar et al. (2010 ▶). For related adamantanyl structural studies, see: El-Emam et al. (2012a ▶,b ▶). For the preparation of one of the precursor molecules, see: El-Emam & Ibrahim (1991 ▶). graphic file with name e-68-o1772-scheme1.jpg

Experimental

Crystal data

2C₂₄H₃₃N₅S·CH₂Cl₂
M _r = 932.17
Orthorhombic,
a = 66.8490 (16) Å
b = 22.1076 (4) Å
c = 6.5109 (1) Å
V = 9622.3 (3) Å³
Z = 8
Cu Kα radiation
μ = 2.38 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.752, T _max = 1.000
18884 measured reflections
4509 independent reflections
4437 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.126
S = 1.09
4509 reflections
299 parameters
19 restraints
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −1.00 e Å⁻³
Absolute structure: Flack (1983 ▶), 1772 Friedel pairs
Flack parameter: −0.002 (17)

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/S1600536812021393/hg5226sup1.cif

e-68-o1772-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812021393/hg5226Isup2.hkl

e-68-o1772-Isup2.hkl^{(221.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812021393/hg5226Isup3.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
C14—H14A⋯S1ⁱ	0.99	2.85	3.803 (3)	162
C16—H16A⋯Cl1	0.99	2.73	3.589 (4)	146

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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. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

supplementary crystallographic information

Comment

In continuation of our interest in the chemical and pharmacological properties of adamantane derivatives, motivated by their putative biological activities (Al-Deeb et al., 2006; Al-Omar et al., 2010), and as part of on-going structural studies (El-Emam et al., 2012a,b), we synthesized the title compound (I) as a potential chemotherapeutic agent. Herein, we describe the crystal and molecular structure of (I).

The asymmetric unit of (I), Fig. 1, comprises an adamantanyl/triazole derivative and half a CH₂Cl₂ molecule of crystallization. In the organic molecule, the piperazinyl ring has a chair conformation and the two N-bound substituents occupy equatorial positions. The piperazinyl residue is almost normal to the triazole ring with the N2—N3—C14—N4 torsion angle being -79.9 (3)°. To a first approximation, the molecule has an L-shape, as found recently in the 2-hydroxybenzylideneamino derivative (El-Emam et al., 2012a).

In the crystal packing, linear supramolecular chains parallel to [001] are formed via C—H···S interactions, Table 1. These are linked into a double chain via C—H···Cl interactions involving the disordered CH₂Cl₂ molecules of solvation, Fig. 2 and Table 1.

Experimental

A mixture of 3-(1-adamantyl)-4-methyl-4H-1,2,4-triazole-5-thiol (499 mg, 2 mmol), prepared according to the literature method (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 635 mg (75%) of the title compound as colourless crystals. M.pt: 423–425 K. Single crystals suitable for X-ray analysis were obtained by slow evaporation of its CH₂Cl₂:EtOH solution held at room temperature (1:1; 5 ml). ¹H NMR (CDCl₃, 500.13 MHz): δ 1.77–1.84 (m, 6H, adamantane-H), 2.14 (s, 6H, adamantane-H), 2.27 (s, 3H, adamantane-H), 3.05 (s, 4H, piperazine-H), 3.27 (s, 4H, piperazine-H), 3.82 (s, 3H, CH₃), 5.20 (s, 2H, CH₂), 6.85–6.93 (m, 3H, Ar—H), 7.25–7.33 (m, 2H, Ar—H). ¹³C NMR (CDCl₃, 125.76 MHz): δ 27.84, 33.97, 36.31, 39.02 (adamantane-C), 31.58 (CH₃), 49.34, 50.40 (piperazine-C), 69.23 (CH₂), 116.27, 119.86, 129.10, 151.33 (Ar—C), 156.31 (triazole C-5), 169.53 (C═S).