Syntheses and crystal structures of two adamantyl-substituted 1,2,4-triazole-5-thione N-Mannich bases

The syntheses and crystal structures of two novel adamantane-substituted N-Mannich bases are reported herein. In the crystals of both compounds, there are C—H⋯F hydrogen bonds present, forming inversion dimers in one and chains in the other.


Supramolecular features
In the crystal of compound (I), molecules are linked by pairs of C-HÁ Á ÁF hydrogen bonds, forming inversion dimers (Table 1 and Fig. 4). In compound (II), molecules are linked by C-HÁ Á ÁF hydrogen bonds, forming chains parallel to the baxis direction. The chains are linked by C-HÁ Á Á interactions, forming layers parallel to the ab plane (Table 2 and

Figure 4
The crystal packing of compound (I), viewed along the c axis. The hydrogen bonds are shown as dashed lines (see Table 1), and only the H atoms involved in these interactions have been included.
Suitable single crystals of compounds (I) and (II) were obtained by slow evaporation of CHCl 3 :EtOH solutions (1:1, 5 ml) at room temperature.

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-[(4-phenylpiperazin-1-yl)methyl]-4,5-dihydro-1H-1,2,4-triazole-5thione (I)
Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 )
x y z U iso */U eq S1 0.97289 (7) 0.79726 (7) 0.53684 (7) 0.0643 (2)    Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.