Mixed Valence Tungsten (IV,V) Compounds with Layered Structures (Part IV): Syntheses,Crystal Structures,and Conductivity of BiX2[W2O2X6] (X = Cl,Br)

The reaction of metallic bismuth with either tungsten tetrachlorideoxide WOCl₄ at 650 K or tungsten tetrabromideoxide WOBr₄ at 670 K, respectively, leads to BiX₂[W₂O₂X₆] (X = Cl, Br) as black, lustrous crystal needles. The crystal structure determinations (triclinic, P$bar{1}$ ) show the two isotypic structures to be closely related to Hg_0.55[W₂O₂Cl₆] with the presence of 1D‐polymeric W₂O₂X₆ double strands. Dinuclear [Bi₂X₄]²⁺ cations are embedded in the host structure via secondary W–X ··· Bi bonds. Unlike the other members of theM_y[W₂O₂X₆] structure family, which crystallize monoclinic and show crystallographic equivalent tungsten atoms, BiX₂[W₂O₂X₆] has independent tungsten sites. Nevertheless, an assignment of an individual oxidation state to the tungsten atoms within the W₂ group (W–W 2.8321(4) Å for X = Cl, 2.8985(4) Å for X = Br) is not possible and a dynamic intervalent state W(IV, V) is assumed. Electrical conductivity measurements for BiCl₂[W₂O₂Cl₆] show semi‐conductive behavior with a very small band gap of 70 meV and a high conductivity of around 0.5 Ω^–1cm^–1 at temperatures above 220 K. A temperature dependence of the activation energy of charge transport is present and interpreted by the Varshni model.