Crystal Chemistry in the Barium Fluoride Chloride System

Abstract

The crystal chemistry of the barium fluoride chloride system is studied both experimentally and theoretically. Different synthetic approaches yield nanocrystalline materials as well as large single crystals. The crystalline phases identified so far are BaFCl, Ba12F19Cl5 and Ba7F12Cl2 (in two modifications) and compared with analogous compounds. It is demonstrated that the compound Ba2F3Cl reported by Fessenden and Lewin 50 years ago corresponds to Ba7F12Cl2. The phase diagram of the BaCl2 – BaF2 system is reinvestigated for fluoride mole fractions between 0.5 and 1. The peritectic formation of Ba12F19Cl5 is observed. Periodic DFT calculations are performed for all structures in this system, including a hypothetical structure for Ba2F3Cl, based on the experimental structure of Ba2H3Cl. The energy of formation of the different barium fluoride chloride compounds from BaCl2 and BaF2 (normalized for one barium atom per formula unit), as calculated by DFT at 0K, is within only about ± 15 kJ/mol. Comparison with recent experimental results on calcium and strontium hydride chloride (bromide) compounds, suggest the possibility of a mutual exclusion between the M2X3Y and M7X12Y2 (M = Ca, Sr, Ba, Pb, X = H, F, Y = Cl,Br) structures. The single crystal structure of PbFBr is also reported

Chemistry of alkaline earth metals: It is not all ionic and definitely not boring!

“…As such, the alkaline earth metal halides very much behave like transition metal halides in organic solvents, hence they do not dissociate and can be used to perform substitution reactions with group 1 metal compounds under salt elimination. Solid state structures of (mixed) halides of barium were recently published with typical coordination number 9 [105]. The gas phase iodides of the heavy alkaline earth metals further show a surprising bent structure, which is the most prominent for BaI 2 , for which it can be stabilized by coordination of neutral donor ligands like THF [106].…”

Crystal growth of La3+-substituted BaCl2 by the micro-pulling-down technique and their luminescence properties

“…The coordination number of Ba ion in BaCl 2 is 9 [21]. As per Shannon's study, the effective ionic radii for Ba 2+ and La 3+ with coordination number 9 are 1.47 and 1.216 Å [20],…”

Facile Preparation of BaClxFy for the Catalytic Dehydrochlorination of 1-Chloro-1,1-Difluoroethane to Vinylidene Fluoride

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