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Correlations involving bond lengths and bond angles in the molecular structure of the Cu4OCl6(4-Mepy)4 complex (4-Mepy = 4-methylpyridine) with four symmetrically independent molecules present in the unit cell showed that the donor-acceptor behavior involving the π-back donation into the pyridine rings of the 4-Mepy ligands is most effectively stimulated by a suitable orientation of the pyridine rings in the trigonal bipyramidal geometry. The pyridine ring planes are almost in parallel orientation with one of the three Cu-Cl bonds. The bond lengths of these Cu-Cl bonds are in a significant linear correlation with the Cu-N bond lengths and the bonds lengths of the pyridine rings. The pyridine rings orientation is affected by distortion of the trigonal bipyramidal geometry to tetragonal pyramidal coordination, by out-of plane pyridine rings deviation and in-plane pyridine rings tilting, by puckering of the pyridine rings and by the effects of the methyl groups. The pyridine rings in at least seven of the sixteen trigonal bipyramidal coordinations exhibit an orientation supporting the π-back bonding between the Cu(II) atoms and the pyridine rings.

chemical papers

Structural and electronic effects involving pyridine rings in 4-methylpyridine Cu4OX6L4 complexes. II. Correlations based on molecular structure of the Cu4OCl6(4-Mepy)4 complex