Halogen complexes coordination geometry

A few thioether-ligated copper(II) complexes have been reported, however (cf. Section 6.6.3.1.2) (417) (essentially square planar), (418) (two crystalline forms one TBP and other SP),361 (419) (SP),362 (420) (SP),362 (421) (TBP),362 (422) (SP),363 (423) (SP),363 (424) (two independent complexes SP and octahedral),364 (425) (TBP).364 In the complexes (420) and (421), EPR spectra revealed that the interaction between the unpaired electron and the nuclear spin of the halogen atom is dependent on the character of the ligand present. For (424) and (425), spectral and redox properties were also investigated. Rorabacher et al.365 nicely demonstrated the influence of coordination geometry upon CV/Cu1 redox potentials, and reported structures of complexes (426) and (427). Both the Cu1 (Section 6.6.4.5.1) and Cu11 complexes have virtual C3v symmetry. 

Tetrachloride and tetrabromide complexes are known for thorium, protactinium, uranium, neptunium, and plutonium. These are similarly produced by halide-based oxidation of metals or hydrides, or by halogenation of oxides. A common structural type is reported for most compounds. The reported structure of thorium tetrachloride reveals that the coordination geometry about the metal is dodecahedral.The compounds are generally volatile and can be sublimed. The gas-phase electron diffraction structure of suggests that the molecule is... 

Compounds of the type M N Fsj (Table 44) are isostructural with NaTZrgFsi, in which the basic coordination geometry about the Zr atom is approximately square antiprismatic, and six antiprisms share corners to form an octahedral cavity which encloses the additional F atom. The complex anions formed with the other halogens are all of the form [MXe] ", with... 

The conclusions reached on the basis of the two complexes H3NICI and HFCIF may be generalized if a monovalent halogen atom acts as an electron donor, its coordination geometry is angular if the halogen atom acts as an electron acceptor, the coordination geometry is linear [9]. 

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