Solvothermal Synthesis And Characterization Of Thioargentates

Chalcogenides are a new class of inorganic materials, and it has attracted considerable attention for a lot of new physical, chemical properties and the complex diversity of their structure. Since the1990s, people have been studying the ternary thioargentates. Up to now, there is only several ternary thioargentates which were synthesized in supercritical ethanediamine at the temperature of300～350℃. In the paper, we use thiophenol as the mineralizer in the low temperature solvothermal system, and obtain three ternary thioargentates, two quaternary thioargentates, as well as a two-dimensional Ag2S crystal.Compound (1) KAg5S3crystallizes in hexagonal system and P-6space group, and the unit cell parameters are a=13.2208(12) A, b=13.2208(12) A, c=7.9479(14) A, a=90°, β=90°,γ=120°.In the structure, the twelve-membered rings composed of sulfur and silver atoms share edges to form layers which are further connected by bridging silver atoms to form3D framework with channels containing K+Compound (2) RbAg5S3crystallizes in hexagonal system and P-62C space group, and the unit cell parameters are a=13.2960(9) A, b=13.2960(9) A, c=8.0060(11) A, α=90°, β=90°, γ=120°. The structure is similar to KAg5S3, and Rb+are located in the open-channel.Compound (3) CsAg7S4crystallizes in tetragonal system and P4/n space group, and the unit cell parameters are a=11.1002(13) A, b=11.1002(13) A, c=8.5310(2) A, α=90°, β=90°, γ=90°. In the structure, sulfur and silver atoms form six-membered rings which further share edges to become eight-membered rings, and four of these infinite stacks of eight-membered rings are connected to each other by bridging sliver atoms to form3D framework with channels where Cs+are located.Compound (4) Ag2S crystallizes in monoclinic system and P2(1)/n space group, and the unit cell parameters are a=4.2469(13) A, b=6.9590(2) A, c=7.8940(2) A, a=90°, β=99.726(4)°, γ=90°.The [AgS3] connect the zigzag chains of-Ag-S-Ag-S-to form2D structure of Ag2S.Compound (5) Na3Ag4Cu5S6crystallizes in tetragonal system and P6(3)/mcm space group, and the unit cell parameters are a=8.4187(10) A, b=8.4187(10)A, c=12.7880(3) A,α=90°. P=90°, γ=90°.In the structure, the unsymmetric structure unit is pseudo octahedra with four opposite faces capped by four sulfur atoms. Those octahedra are linked through two S-Ag covalent bonds to form3D framework with Na+in the open-channel.Compound(6)KAg2Cu3S crystallizes in hexagonal system and P6(3)/mcm space group, and the unit cell parameters are a=7.6487(10)A,b=7.6487(10)A,c=7.4610(2)A,；；α=90°,β=90°,γ=120°The structure of KAg2Cu3S is also similar to KAg5S3,and K+are1ocated in the open-channel.