Solid zirconium bromides

ZrBr4 ZIRCONIUM BROMIDE 70.795 3.5625E-01 -8.1803E-04 8.8208E-07 -3.6360E-10 298 720 solid... 

Wijeyesekera, S. D. Corbett, J. D. (1985). A Neutron Powder Diffraction Study of Zirconium Bromide Deuteride, ZrBrD. Two Hydrogen Atoms in the Same Metal Interstice, Solid State Common. 54, 657 - 660. 

Zirconium(IV) and hafnium(IV) chlorides and bromides form 1 2 adducts of the type [ZrX4(RCN)2] (R = Me, Et, Pr or Ph X = Cl or Br) and [HfX4(MeCN)2] (X = Cl or Br).11SM24 These complexes may be prepared by (i) direct reaction of the metal tetrahalide with an excess of the nitrile120 123 or (ii) electrochemical oxidation of zirconium or hafnium metal in the presence of a solution of chlorine or bromine in acetonitrile.118 The adducts are moisture-sensitive, white solids, insoluble in nonpolar solvents, but soluble in acetonitrile. In the later solvent, [ZrBr4(MeCN)2 behaves as a nonelectrolyte.122... 

The molar volumes and liquid-gas phase compositions for the ZrCl -HfCl4 systems have also been studied (144). Nisel son (396) found that the binary systems of zirconium-hafnium chlorides, and bromides and iodides as well, have unlimited solubility in the liquid and solid states. The systems ZrCl4-ZrBr4 and ZrCl4-Zrl4 form a continuous series of solid solutions which contains a minimum. No mention is made of the possibility of mixed halide species. 

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