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The crystal structures of four compounds - 4'-[2-(tosylamino)benzylideneamino]-2,3-benzo-15-crown-5 (HL), ZnL2, CuL2 and LiNCS·HL, two of which (CuL2 and LiNCS·HL) being determined from synchrotron powder diffraction data - were used in DFT calculations to determine a possible reason for the different ionic selectivities of ZnL2 and CuL2 complexes.
organic compounds
Crystallization of the hexane reaction mixture after treatment of LiGe(OCH2CH2NMe2)3 with Ph3CN3 gives rise to a new triclinic (space group P
) polymorph of triphenylmethylamine, C19H17N, (I), containing dimers formed by N—H
N hydrogen bonds, whereas the structure of the known orthorhombic (space group P212121) polymorph of this compound, (II), consists of isolated molecules. While the dimers in (I) lie across crystallographic inversion centres, the molecules are not truly related by them. The centrosymmetric structure is due to the statistical disordering of the amino H atoms participating in the N—HN hydrogen-bonding interactions, and thus the inversion centre is superpositional. The conformations and geometric parameters of the molecules in (I) and (II) are very similar. It was found that the polarity of the solvent does not affect the capability of triphenylmethylamine to crystallize in the different polymorphic modifications. The orthorhombic polymorph, (II), is more thermodynamically stable under normal conditions than the triclinic polymorph, (I). The experimental data indicate the absence of a phase transition in the temperature interval 120–293 K. The densities of (I) (1.235 Mg m−3) and (II) (1.231 Mg m−3) at 120 K are practically equal. It would seem that either the kinetic factors or the effects of the other products of the reaction facilitating the hydrogen-bonded dimerization of triphenylmethylamine molecules are the determining factor for the isolation of the triclinic polymorph (I) of triphenylmethylamine.
) polymorph of triphenylmethylamine, C19H17N, (I), containing dimers formed by N—HN hydrogen bonds, whereas the structure of the known orthorhombic (space group P212121) polymorph of this compound, (II), consists of isolated molecules. While the dimers in (I) lie across crystallographic inversion centres, the molecules are not truly related by them. The centrosymmetric structure is due to the statistical disordering of the amino H atoms participating in the N—HN hydrogen-bonding interactions, and thus the inversion centre is superpositional. The conformations and geometric parameters of the molecules in (I) and (II) are very similar. It was found that the polarity of the solvent does not affect the capability of triphenylmethylamine to crystallize in the different polymorphic modifications. The orthorhombic polymorph, (II), is more thermodynamically stable under normal conditions than the triclinic polymorph, (I). The experimental data indicate the absence of a phase transition in the temperature interval 120–293 K. The densities of (I) (1.235 Mg m−3) and (II) (1.231 Mg m−3) at 120 K are practically equal. It would seem that either the kinetic factors or the effects of the other products of the reaction facilitating the hydrogen-bonded dimerization of triphenylmethylamine molecules are the determining factor for the isolation of the triclinic polymorph (I) of triphenylmethylamine.
