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- W2000354311 abstract "Thiosilicates of the Rare-Earth Elements: III. KLa[SiS4] and RbLa[SiS4] – A Structural Comparison Pale yellow, platelet shaped, air- and water resistant single crystals of KLa[SiS4] derived from the reaction of lanthanum (La) and sulfur (S) with silicon disulfide (SiS2) in a molar ratio of 2 : 3 : 1 with an excess of potassium chloride (KCl) as flux and source of potassium ions in evacuated silica ampoules at 850 °C within seven days. The analogous reaction utilizing a melt of rubidium chloride (RbCl) instead also leads to yellow comparable single crystals of RbLa[SiS4]. The potassium lanthanum thiosilicate crystallizes monoclinically with the space group P21/m (a = 653.34(6), b = 657.23(6), c = 867.02(8) pm, β = 107.496(9)°) and two formula units per unit cell, while the rubidium lanthanum thiosilicate has to be assigned orthorhombically with the space group Pnma (a = 1728.4(2), b = 667.23(6), c = 652.89(6) pm) and four formula units in its unit cell. In both compounds the La3+ cations are surrounded by 8+1 sulfide anions in the shape of tricapped trigonal prisms. The Rb+ cations in RbLa[SiS4] show a coordination number of 9+2 relative to the S2− anions, which form pentacapped trigonal prisms about Rb+. This coordination number, however, is apparently too high for the K+ cations in KLa[SiS4], so that they only exhibit a bicapped trigonal prismatic environment built up by eight S2− anions. The isolated thiosilicate tetrahedra [SiS4]4− of the rubidium compound are surrounded by La3+ both edge- and face-capping, but terminal as well as edge- and face-spanning by Rb+. In the potassium compound there is no change for the La3+ environment about the [SiS4]4− tetrahedra, but the K+ cations are only able to attach terminal and via edges. The whole structure is built up by anionic equation/tex2gif-stack-1.gif{La[SiS4]}− layers that are separated by the alkali metal cations. In direct comparison the two thiosilicate structures can be regarded as stacking variants." @default.
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- W2000354311 date "2005-06-01" @default.
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- W2000354311 title "Thiosilicate der Selten-Erd-Elemente: III. KLa[SiS4] und RbLa[SiS4] - Ein struktureller Vergleich" @default.
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- W2000354311 doi "https://doi.org/10.1002/zaac.200400528" @default.
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!["Thiosilicates of the Rare-Earth Elements: III. KLa[SiS4] and RbLa[SiS4] – A Structural Comparison Pale yellow, platelet shaped, air- and water resistant single crystals of KLa[SiS4] derived from the reaction of lanthanum (La) and sulfur (S) with silicon disulfide (SiS2) in a molar ratio of 2 : 3 : 1 with an excess of potassium chloride (KCl) as flux and source of potassium ions in evacuated silica ampoules at 850 °C within seven days. The analogous reaction utilizing a melt of rubidium chloride (RbCl) instead also leads to yellow comparable single crystals of RbLa[SiS4]. The potassium lanthanum thiosilicate crystallizes monoclinically with the space group P21/m (a = 653.34(6), b = 657.23(6), c = 867.02(8) pm, β = 107.496(9)°) and two formula units per unit cell, while the rubidium lanthanum thiosilicate has to be assigned orthorhombically with the space group Pnma (a = 1728.4(2), b = 667.23(6), c = 652.89(6) pm) and four formula units in its unit cell. In both compounds the La3+ cations are surrounded by 8+1 sulfide anions in the shape of tricapped trigonal prisms. The Rb+ cations in RbLa[SiS4] show a coordination number of 9+2 relative to the S2− anions, which form pentacapped trigonal prisms about Rb+. This coordination number, however, is apparently too high for the K+ cations in KLa[SiS4], so that they only exhibit a bicapped trigonal prismatic environment built up by eight S2− anions. The isolated thiosilicate tetrahedra [SiS4]4− of the rubidium compound are surrounded by La3+ both edge- and face-capping, but terminal as well as edge- and face-spanning by Rb+. In the potassium compound there is no change for the La3+ environment about the [SiS4]4− tetrahedra, but the K+ cations are only able to attach terminal and via edges. The whole structure is built up by anionic equation/tex2gif-stack-1.gif{La[SiS4]}− layers that are separated by the alkali metal cations. In direct comparison the two thiosilicate structures can be regarded as stacking variants."](?object=%22Thiosilicates%20of%20the%20Rare-Earth%20Elements%3A%20III.%20KLa%5BSiS4%5D%20and%20RbLa%5BSiS4%5D%20%E2%80%93%20A%20Structural%20Comparison%20Pale%20yellow%2C%20platelet%20shaped%2C%20air-%20and%20water%20resistant%20single%20crystals%20of%20KLa%5BSiS4%5D%20derived%20from%20the%20reaction%20of%20lanthanum%20(La)%20and%20sulfur%20(S)%20with%20silicon%20disulfide%20(SiS2)%20in%20a%20molar%20ratio%20of%202%20%3A%203%20%3A%201%20with%20an%20excess%20of%20potassium%20chloride%20(KCl)%20as%20flux%20and%20source%20of%20potassium%20ions%20in%20evacuated%20silica%20ampoules%20at%20850%20%C2%B0C%20within%20seven%20days.%20The%20analogous%20reaction%20utilizing%20a%20melt%20of%20rubidium%20chloride%20(RbCl)%20instead%20also%20leads%20to%20yellow%20comparable%20single%20crystals%20of%20RbLa%5BSiS4%5D.%20The%20potassium%20lanthanum%20thiosilicate%20crystallizes%20monoclinically%20with%20the%20space%20group%20P21%2Fm%20(a%20%3D%20653.34(6)%2C%20b%20%3D%20657.23(6)%2C%20c%20%3D%20867.02(8)%20pm%2C%20%CE%B2%20%3D%20107.496(9)%C2%B0)%20and%20two%20formula%20units%20per%20unit%20cell%2C%20while%20the%20rubidium%20lanthanum%20thiosilicate%20has%20to%20be%20assigned%20orthorhombically%20with%20the%20space%20group%20Pnma%20(a%20%3D%201728.4(2)%2C%20b%20%3D%20667.23(6)%2C%20c%20%3D%20652.89(6)%20pm)%20and%20four%20formula%20units%20in%20its%20unit%20cell.%20In%20both%20compounds%20the%20La3%2B%20cations%20are%20surrounded%20by%208%2B1%20sulfide%20anions%20in%20the%20shape%20of%20tricapped%20trigonal%20prisms.%20The%20Rb%2B%20cations%20in%20RbLa%5BSiS4%5D%20show%20a%20coordination%20number%20of%209%2B2%20relative%20to%20the%20S2%E2%88%92%20anions%2C%20which%20form%20pentacapped%20trigonal%20prisms%20about%20Rb%2B.%20This%20coordination%20number%2C%20however%2C%20is%20apparently%20too%20high%20for%20the%20K%2B%20cations%20in%20KLa%5BSiS4%5D%2C%20so%20that%20they%20only%20exhibit%20a%20bicapped%20trigonal%20prismatic%20environment%20built%20up%20by%20eight%20S2%E2%88%92%20anions.%20The%20isolated%20thiosilicate%20tetrahedra%20%5BSiS4%5D4%E2%88%92%20of%20the%20rubidium%20compound%20are%20surrounded%20by%20La3%2B%20both%20edge-%20and%20face-capping%2C%20but%20terminal%20as%20well%20as%20edge-%20and%20face-spanning%20by%20Rb%2B.%20In%20the%20potassium%20compound%20there%20is%20no%20change%20for%20the%20La3%2B%20environment%20about%20the%20%5BSiS4%5D4%E2%88%92%20tetrahedra%2C%20but%20the%20K%2B%20cations%20are%20only%20able%20to%20attach%20terminal%20and%20via%20edges.%20The%20whole%20structure%20is%20built%20up%20by%20anionic%20equation%2Ftex2gif-stack-1.gif%7BLa%5BSiS4%5D%7D%E2%88%92%20layers%20that%20are%20separated%20by%20the%20alkali%20metal%20cations.%20In%20direct%20comparison%20the%20two%20thiosilicate%20structures%20can%20be%20regarded%20as%20stacking%20variants.%22){kind=link}