RESUMEN
Two copper complex solvatomorphs, namely (3,10-C-meso-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane)bis(perchlorato-κO)copper(II) 1.2-hydrate, [Cu(ClO4)2(C18H40N4)]·1.2H2O, (I), and (3,10-C-meso-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane)bis(perchlorato-κO)copper(II), [Cu(ClO4)2(C18H40N4)], (II), are described and compared with each other and with a third, already reported, anhydrous diastereomer, denoted (III). Both compounds present very similar centrosymmetic coordination environments, with the Cu(II) cation lying on an inversion centre in a distorted 4+2 octahedral environment, defined by the macrocyclic N4 group in the equatorial sites and two perchlorate groups in trans-axial positions [one of the perchlorate ligands in (I) is partially disordered]. The most significant difference in molecular shape is seen in the orientation of the perchlorate anions, and the influence of this on the intramolecular hydrogen bonding is discussed. The (partially) hydrated state of (I) favours the formation of chains along [011], while the anhydrous character of (II) and (III) promotes loosely bound structures with low packing indices.
Asunto(s)
Complejos de Coordinación/química , Cobre/química , Cristalografía por Rayos X , Enlace de Hidrógeno , Ligandos , Modelos Moleculares , Estructura Molecular , Solventes/química , EstereoisomerismoRESUMEN
The complete cation in the title hydrated mol-ecular salt, [Ni(CH(3)CO(2))(C(16)H(36)N(4))]ClO(4)·H(2)O, is generated by the application of crystallographic twofold symmetry; the perchlorate anion and water mol-ecule are each disordered around a twofold axis. The Ni(II) atom exists within a cis-N(4)O(2) donor set based on a strongly distorted octa-hedron and defined by the four N atoms of the macrocyclic ligand and two O atoms of a symmetrically coordinating acetate ligand. In the crystal, hydrogen bonding (water-acetate/perchlorate O-Hâ¯O and amine-perchlorate N-Hâ¯O) leads to layers in the ab plane. The layers stack along the c axis, being connected by C-Hâ¯O(water) inter-actions. The crystal studied was found to be a non-merohedral twin; the minor component refined to 15.9â (6)%.
RESUMEN
The Cd(II) atom in the title complex, [Cd(NO(3))(C(18)H(40)N(4))]NO(3)·0.5H(2)O, is coordinated within a cis-N(4)O(2) donor set provided by the tetra-dentate macrocyclic ligand and two O atoms of a nitrate anion; the coordination geometry is distorted octa-hedral. The lattice water mol-ecule is located on a twofold rotation axis. N-Hâ¯O hydrogen bonds and weak C-Hâ¯O inter-actions link the complex cations into a supra-molecular layer in the bc plane. Layers are connected by O-Hâ¯O hydrogen bonds between the lattice water mol-ecule and the non-coordinating nitrate anion, as well as by weak C-Hâ¯O contacts.
RESUMEN
In the title hydrated salt, C(16)H(38)N(4) (2+)·2ClO(4) (-)·H(2)O, the dication is protonated at the diagonally opposite N atoms proximate to the -C(CH(3))(2)- groups. Within the cavity, there are two ammonium-amine N-Hâ¯N hydrogen bonds. Supra-molecular layers are formed in the crystal packing whereby the water mol-ecule links two perchlorate anions, and the resultant aggregates are connected to the dications via N-Hâ¯O hydrogen bonds. Layers, with an undulating topology, stack along the a axis being connected by C-Hâ¯O inter-actions.