Abstract
In divalent tin halides, when the halogen is small and highly electronegative (F, Cl), the tin valence orbitals are hybridized, the tin(II) non-bonded electron pair is located on one of the hybrid orbitals, and the resulting large electric field gradient gives a large quadrupole splitting. The reaction of barium chloride and tin difluoride in aqueous solutions, for large BaCl2.2H2O/SnF2 ratios (>10) results in the precipitation of a white powdered material, which is identified by X-ray diffraction to be BaCIF. However, Tin-119 Mossbauer spectroscopy shows the material contains a fairly large amount of divalent tin in the Sn2+ ionic form, with unhybridized orbitals, like in SnCl2. Using X-ray diffraction, we have established that Sn2+ ions substitute 15% of the Ba2+ ions at random, and chemical analysis shows the material has the formula Ba5.66SnCl7.30F6.04 and thus is enriched in chlorine.
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