Abstract
AbstractMelting reactions of Cu, CuCl, Q (Q = S, Se), and Bi2Q3 yield black, shiny needles of the chalcogenide chlorides Cu9Bi9S16Cl8 or Cu7.4Bi6Se12Cl7. The compounds decompose peritectically above 612(5) K and 623(5) K. Raman spectra reveal the presence of dichalcogenide groups, whereas for copper the oxidation state +I is supported by Cu‐K‐XANES. Cu9Bi9S16Cl8 crystallizes in the monoclinic space group C2/m with a = 2061.6(3) pm, b = 394.89(3) pm, c = 1194.1(2) pm, β = 102.98(1) °, T = 293(2) K. Three sulfide and four chloride anions coordinate each of the two independent bismuth cations in the shape of monocapped trigonal prisms. The [BiS3Cl4] polyhedra form quadruple rods by sharing edges and faces. Covalent bonds between sulfide anions connect the rods into layers parallel to (001). Disordered copper as well as bismuth cations fill the voids between the layers. The Joint Probability Density Function (JPDF) reveals a continuous pathway along [010], which might be used for ion conduction. Cu7.4Bi6Se12Cl7 crystallizes in the hexagonal space group P6/m with a = 1505.8(1) pm, c = 401.41(3) pm, T = 293(2) K. Monocapped trigonal prisms [BiSe3Cl4] share faces along [001]. Through edge‐sharing these rods form hexagonal tubes, which are filled with disordered copper cations as well as chloride anions. Diselenide bridges link neighboring tubes. The intertubular channels contain stationary copper cations.
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