Please use this identifier to cite or link to this item:
|Title:||Syntheses, structures, and properties of six novel alkali metal tin sulfides: K2Sn2S8, α-Rb2Sn2S8, β-Rb2Sn2S8, K2Sn2S5, Cs2Sn2S6, and Cs2SnS14||Authors:||Kanatzidis, Mercouri G.
|Keywords:||Chemistry;Alkali metal compounds;Sulfides;Polysulfides;Chemicals;Compounds;Ligands||Issue Date:||1993||Publisher:||ACS Publications||Source:||Inorganic chemistry, 1993, volume 32, issue 11, pages 2453-2462||Abstract:||Six alkali metal tin polysulfides and one monosulfide, K2Sn2S8 (I), α-Rb2Sn2S8 (II), β-Rb2Sn2S8 (III), K2Sn2S5 (IV), Cs2Sn2S6 (V), and Cs2SnS14 (VI), respectively, were synthesized by a molten salt technique. I and IV were made by heating mixtures of Sn/K2S/S (molar ratio 1/2/8) at 275 and 320°C, respectively, for 4-6 days. II and III were made by heating mixtures of Sn/Rb2S/S (molar ratio 1/2/12 for II and 1/1/8 for III at 330 and 450°C, respectively, for 4-6 days. V and VI were made by heating mixtures of Sn/Cs2S/S (molar ratio 1/3/8 for V and 1/2/8-12 for VI at 275°C for 4-6 days. The crystals form in a K2Sx, Rb2Sx, and Cs2Sx flux, respectively. Orange crystals of I crystallize in the monoclinic space group P21/n with a = 9.580(8) Å, b = 10.004(5) Å, c = 14.131(7) Å, β = 107.82(6)°, and Z = 4. Orange crystals of II and III have the same anionic frameworks as I. II crystallizes also in the monoclinic space group P21/n with a = 9.788(3) Å, b = 9.978(3) Å, c = 14.360(2) Å, and β = 106.70(2)°, and Z = 4. III crystallizes in the orthorhombic space group Pbcn with a = 9.987(5) Å, b = 19.635(3) Å, c = 13.747(3) Å, and Z = 8. The yellow-orange IV crystallizes in the monoclinic space group C2/c with a = 11.804(3) Å, b = 7.808(1) Å, c = 11.539(1) Å, β = 108.35(1)°, and Z = 4. The yellow V crystallizes in the triclinic space group P1 with a = 7.289(4) Å, b = 7.597(3) Å, c = 6.796(3) Å, α = 114.80(3)°, β = 108.56(4)°, γ = 97.54(4)°, and Z = 1. Red crystals of VI are monoclinic, space group P21/n, with a = 6.964(6) Å, b = 18.66(1) Å, c = 14.80(1) Å, β = 99.39(1)°, and Z = 4. The structures of these six compounds have been determined by single-crystal X-ray diffraction analysis. IR and Raman spectra for these compounds are reported. I-III have novel two-dimensional structures. Each [Sn2S8]n2n- layer is composed of [Sn2S4]n parallel chains, which contain octahedral SnS6 and tetrahedral SnS4, cross-linked by S42- ligands. Charge-compensating potassium or rubidium cations are found between the layers. IV has the Tl2Sn2S3 structure type and has a three-dimensional structure, with [SnS3]n2n- chains formed by distorted SnS5 trigonal bipyramids sharing two of their common edges with one another. Those chains are then cross-linked by sharing the remaining vertices of the trigonal bipyramids to generate parallel tunnels in which potassium cations are located. The structure of V is closely related to IV. It also comprises [SnS3]n2n- chains which in a different fashion are cross-linked by S22- to form an extended two-dimensional structure. VI contains a molecular [SnS14]2- complex anion with octahedral Sn4+ ligated by two S42- and one S62- chelating ligands. The UV/vis optical properties of I-V are reported. The optical band gaps are 2.15 eV for I-III, 2.36 eV for IV, and 2.44 eV for V||URI:||http://ktisis.cut.ac.cy/handle/10488/6677||ISSN:||00201669||DOI:||10.1021/ic00063a042||Rights:||© 1993 American Chemical Society||Type:||Article|
|Appears in Collections:||Άρθρα/Articles|
Show full item record
checked on Dec 14, 2018
WEB OF SCIENCETM
checked on Feb 15, 2019
checked on Feb 20, 2019
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.