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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >CRYSTAL STRUCTURE AND PROPERTIES OF CALCIUM AND STRONTIUM HEXATHIODIPHOSPHATE(IV), CA2P2S6 AND SR2P2S6, WITH A CONTRIBUTION ON CA5P3 AND PB2P2S6 [German]
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CRYSTAL STRUCTURE AND PROPERTIES OF CALCIUM AND STRONTIUM HEXATHIODIPHOSPHATE(IV), CA2P2S6 AND SR2P2S6, WITH A CONTRIBUTION ON CA5P3 AND PB2P2S6 [German]

机译:六硫代磷酸二氢钙和锶(IV),CA2P2S6和SR2P2S6的晶体结构和性质,对CA5P3和PB2P2S6的贡献[德国]

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Ca2P2S6 and Sr2P2S6 were prepared from metal and a mixture of red phosphorus and sulfur (molar ratio M:P:S=1:1:3)in 2 corundum crucibles inserted in quartz ampullae under vacuum (20 d 900 degrees C). The compounds were obtained as colourless, crystalline powders containing single crystals. They crystallize in the Sn2P2S6 (high temperature form) type structure (P2(1)/c, Z=2): Ca2P2S6 a=653.2(2) pm, b=728.1(2)pm, c=1110.1(4)pm, beta=124.00(4)degrees, d(4)(25)=2.50(2); Sr2P2S6 a=664.3(2)pm, b=755.7(3)pm, c=1139.7(3) pm, beta=124.07(2)degrees, d(4)(25)=2.97(2). The anions P2S64- have staggered confirmation and are arranged with the motif of a cubic close-packing. Sr2+ is coordinated by 8S which form a twofold face-capped trigonal prism and belong to 4P(2)S(6)(4-). Structure calculations clearly show that Pb2P2S6 also crystallizes in P2(1)/c and not in Pc [1]. Also, Raman- and IR-spectra of Ca5P1 were recorded at 20 degrees C. The stretching vibrations of P-8(10-) were assigned in analogy to those of P2S64- in alkaline earth hexathiodiphosphates(IV). The range of their frequencies (480 to 340 cm(-1)) is essentially smaller and shifted to smaller values compared with P2S64- in Ca2P2S6 and Sr2P2S6 (620 to 390 cm(-1)). The symmetry of P-4(10-) is not D-3d but C-2h as in the case of P2S64-. [References: 14]
机译:Ca2P2S6和Sr2P2S6是由金属和红磷与硫的混合物(摩尔比M:P:S = 1:1:3)在真空(20 d 900摄氏度)下插入石英壶瓶的2个刚玉坩埚中制备的。获得的化合物为含有单晶的无色结晶粉末。它们以Sn2P2S6(高温形式)型结构结晶(P2(1)/ c,Z = 2):Ca2P2S6 a = 653.2(2)pm,b = 728.1(2)pm,c = 1110.1(4)pm, beta = 124.00(4)度,d(4)(25)= 2.50(2); Sr2P2S6 a = 664.3(2)pm,b = 755.7(3)pm,c = 1139.7(3)pm,beta = 124.07(2)度,d(4)(25)= 2.97(2)。阴离子P2S64-具有交错确认,并以立方紧密堆积的图案排列。 Sr2 +由8S协调,该8S形成了一个具有两个面封顶的三角棱镜,并属于4P(2)S(6)(4-)。结构计算清楚地表明,Pb2P2S6也以P2(1)/ c而不是Pc结晶[1]。另外,在20摄氏度下记录了Ca5P1的拉曼光谱和红外光谱。与在碱土金属六硫代二磷酸酯(IV)中的P2S64-相似,将P-8(10-)的拉伸振动归类。与Ca2P2S6和Sr2P2S6中的P2S64-(620至390 cm(-1))相比,它们的频率范围(480至340 cm(-1))本质上较小,并且移至较小的值。与P2S64-一样,P-4(10-)的对称性不是D-3d,而是C-2h。 [参考:14]

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