Constitutional Isomerism of BiW 6 Cl 15 : (BiCl)[W 6 Cl 14 ] and (BiCl 2 )[W 6 Cl 13 ]

The compound (BiCl)[W 6 Cl 14 ] was previously characterized as a product of the reduction of tungsten hexachloride with elemental bismuth. Another modification of BiW 6 Cl 15 is now presented as (BiCl 2 )[W 6 Cl 13 ], based on the results of an X‐ray single crystal structure determination (space group P 2 1 / c , a = 1354.3(2) pm, b = 1234.4(2) pm, c = 1538.9(2) pm, and β = 118.76(1) °). The structure of (BiCl 2 )[W 6 Cl 13 ] contains chains of [(W 6 Cl 8 i )Cl 4 a Cl 2/2 a–a ] – clusters bridged by chlorine atoms. The (BiCl 2 ) + counterion exhibits two short Bi–Cl distances of 244.1(4) and 245.9(3) pm, respectively.