Cu₇Bi₆S₁₀Cl₅ – Mobile Copper(I) Cations Inside Dendritic Channels of a Rigid Framework  

Abstract

Abstract. The melting reaction of Cu, CuCl, S, and Bi 2 S 3 yields black, shiny needles of the sulfide chloride Cu 7 Bi 6 S 10 Cl 5 . The compound decomposes peritectically above 639(5) K. Cu-K-XANES data confirm the oxidation state +I of Cu. Cu 7 Bi 6 S 10 Cl 5 crystallizes in the monoclinic space group C2/m with a = 2878.3(9) pm, b = 396.59 (9)

Copper Bismuth Chalcogenide Halogenides with Extensively Disordered and Mobile Copper(I) Cations

“…Mixed Cu/Bi occupancy in networksof octahedra was also found in the minerals hodrushite(Cu 8 Bi 12 S 22 )7 and cuprobismutite (Cu 10 Bi 12 S 23 ),8 as well as in synthetic compounds such as Cu 9 BiS 6 ,9 the pavonitehomologues Cu 1.77 Bi 4.57 S 8 10 and Cu 2.93 Bi 4.79 S 9 ,11 andCu 1.57 Bi 2.37 Se 2.68 Br 3.32 4g. On the other hand, there are numerous related compounds, predominantly chalcogenide halogenides, with various structure types, in which copper does not occupy the bismuth sites, such as CuBiSCl 2 ,4cCu 9 Bi 9 S 16 Cl 8 ,4e Cu 7.4 Bi 6 Se 12 Cl 7 ,4e Cu 7 Bi 6 S 10 Cl 5 ,4fCu 22 Bi 12 S 21 Cl 16 ,4h Cu 3 BiS 2 Br 2 ,4i and Cu 4 Bi 3 S 5 Br 1.81 Cl 1.19 4i…”