The Deformation of Di-μμ-halide Dinuclear Five-Coordinate Copper(II) Complexes in the Crystalline State

Abstract

The coordination geometries of 154 dinuclear di-/zchloro, di-#-bromo and di-/z-fluoro five-coordinate (4 + 1) copper(II) complexes have been analyzed by the structural correlation method. Two reference Cu n polyhedra have been established: (i) a trigonal bipyramid (TBP) in which the equatorial bond lengths are equal, but with the symmetry at the metal often deformed from D3h to C2, and (ii) an elongated square pyramid (SQP), with either a pyramidally or tetrahedrally distorted base, in which the trans valence angles are equal. Six different paths for the SQP~TBP deformation of the Cu n coordination have been established from three criteria: (a) the location of the bridging ligands (axial and equatorial or equatorial and equatorial in TBP); (b) the nature of the deformation of the SQP base plane (pyramidal or tetrahedral); (c) whether a bridging or nonbridging bond is elongated in a SQP. The causes of the angular distortions from C 2 symmetry along the apical bond of a SQP, typical for the TBP~SQP Berry path, are analyzed. A progressive reduction of the tetragonal elongation of the Cu--D apical (SQP) bond length along the SQP~,-~-TBP transformation path and trigonal equalization of the three equatorial Cu--D (TBP) bonds are observed. The dependence of the average Cu--Cu' distance and Cu--X--Cu' angles on the deformation path are also established.

Zinc(II) Complexes with Amino Acids for Potential Use in Dermatology: Synthesis, Crystal Structures, and Antibacterial Activity

“…The chelating glycine-ligands are arranged in the trans configuration. According to bond angles around the Zn cations, each basal plane of SQP is tetrahedrally distorted [32]: two trans oriented oxygen atoms lie above the best least-squares plane (N 2 O 2 ), whereas two trans oriented nitrogen atoms are below it. The zinc cations sit 0.5 Å above the best plane toward the apical atom (Table S2).…”