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Reactions of zinc chloride with beryllium chloride in the molar ratios of 1:1 and 3:2 at  T  = 300°C in sealed ampoules lead to the formation of the two compounds Be 1−   x  Zn  x  Cl 2  ( x  = 0.563(2) and 0.489(3), respectively). Their composition and crystal structures were evidenced by single crystal X-ray structure analysis. Both compounds crystallize isotypic to  β -BeCl 2  in the tetragonal space group  I 4 1 / acd , No. 142,  tI 96, with  a  = 10.7548(1),  c  = 19.4656(5) Å,  V  = 2251.50(7) Å 3 ,  Z  = 32 at  T  = 100 K for the first and  a  = 10.7511(3),  c  = 19.2335(10) Å,  V  = 2223.1(2) Å 3 ,  Z  = 32 at  T  = 100 K for the second compound. The positions of the Be atoms are mixed-occupied by Zn atoms. The compounds were additionally characterized by powder X-ray diffraction and infrared spectroscopy. Plots according to Vegard’s law allowed for extrapolation towards a neat ZnCl 2  phase that would crystallize in the  β -BeCl 2  structure, which is the ZnI 2  structure type. Quantum chemical calculations have confirmed that such a ZnCl 2  modification would represent a true local minimum.

A brief visit to the BeCl 2 /ZnCl 2 system and the prediction of a new polymorph of ZnCl 2