3-(Adamantan-1-yl)-4-methyl-1-({4-[3-(trifluoromethyl)phenyl]piperazin-1-yl}methyl)-4,5-dihydro-1H-1,2,4-triazole-5-thione

In the title compound, C25H32F3N5S, two independent molecules comprise the asymmetric unit and are related across a pseudo-centre of inversion. The piperazine rings have chair conformations with each N-bound substituent occupying an equatorial position so that the dihedral angles between the planes of the triazole and benzene ring are 78.20 (19) and 79.10 (19)° for the two independent molecules, indicating that the molecules have an L-shape. In the crystal, a three-dimensional architecture is stabilized by C—H⋯π interactions. The crystal studied was an inversion twin with the fractional contribution of the minor component being 0.27 (9).

In the title compound, C 25 H 32 F 3 N 5 S, two independent molecules comprise the asymmetric unit and are related across a pseudo-centre of inversion. The piperazine rings have chair conformations with each N-bound substituent occupying an equatorial position so that the dihedral angles between the planes of the triazole and benzene ring are 78.20 (19) and 79.10 (19) for the two independent molecules, indicating that the molecules have an L-shape. In the crystal, a threedimensional architecture is stabilized by C-HÁ Á Á interactions. The crystal studied was an inversion twin with the fractional contribution of the minor component being 0.27 (9).  Table 1 Hydrogen-bond geometry (Å , ).

D-HÁ
Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/03).

Tiekink Comment
In connection with the biological activities of adamantane derivatives (Al-Deeb et al., 2006;Al-Omar et al., 2010) and complementary structural studies (El-Emam et al., 2012), the title compound was synthesized and characterized, including by X-ray crystallography.
Two independent molecules comprise the crystallographic asymmetric unit of (I), Fig. 1. The molecules are related across a pseudo centre of inversion. As shown in Fig. 2, the best fit between the molecules occurs when the inverted S2containing molecule is superimposed upon the S1-containing molecule. Each piperazinyl ring has a chair conformation with the respective N-bound methylene and benzene ring substituents in equatorial positions. With respect to the triazole ring, the piperazinyl ring lies completely to one side with the N2-N3-C14-N4 torsion angle being -58.5 (5)°; for the S2-containing molecule, the equivalent N7-N8-C39-N9 torsion angle is 63.9 (5)°. The dihedral angles between the triazole and benzene rings are 78.20 (19) and 79.10 (19)° for the S1-and S2-containing molecules, respectively, so that overall, each molecule approximates the shape of the letter L.
The crystal packing of (I) is dominated by C-H···π interactions, Table 1, where the triazole and benzene rings of both independent molecules function as the π-systems; the benzene ring of the S1-containing molecule is bifurcated. These interactions result in a three-dimensional architecture, Fig. 3.

Figure 1
The molecular structures of the two independent molecules comprising the asymmetric unit of (I) showing the atomlabelling scheme and displacement ellipsoids at the 35% probability level. Overlay diagram of the S1-(red image) and inverted S2-containing molecules (blue) where the triazole rings have been superimposed.
supplementary materials

Figure 3
View of the unit-cell contents in projection down the b axis of (I). The C-H···π contacts are shown as purple dashed lines.   (9) Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.