Neue Sulfido-Antimonate der schweren Alkalimetalle: Synthese, Kristallstruktur und chemische Bindung von (K=Rb=Cs)3SbS3 und Cs3SbS4 · H2O / New Sulfido Antimonates of the Heavy Alkali Metals: Synthesis, Crystal Structure and Chemical Bonding of (K=Rb=Cs)3SbS3 and Cs3SbS4 · H2O
Neue Sulfido-Antimonate der schweren Alkalimetalle: Synthese, Kristallstruktur und chemische Bindung von (K=Rb=Cs)3SbS3 und Cs3SbS4 · H2O / New Sulfido Antimonates of the Heavy Alkali Metals: Synthesis, Crystal Structure and Chemical Bonding of (K=Rb=Cs)3SbS3 and Cs3SbS4 · H2O
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DOI：
10.5560/znb.2013-3227
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发表时间：
2013-12
期刊：
影响因子：
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通讯作者：
L. Schindler;M. Schwarz;C. Röhr
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文献类型：
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作者：
L. Schindler;M. Schwarz;C. Röhr
以碱金属硫化物Rb2S=Cs2S2和单质锑、硫或Sb2S3为原料，在700℃左右的反应温度下制备了新型硫锑酸盐（III） （Rb=Cs）3SbS3。已知的同型钾化合物也是类似地由这些元素合成的。使用单晶x射线数据对浅黄色晶体的结构进行了细化。两种化合物均与各自的Na盐同型，形成Na3AsS3结构类型(立方，空间群P213， K/Rb/Cs: a = 947:21(7)=982:28（5)=1025:92(5) pm, Z = 4, R1 = 0:0159=0:0560=0:0582）。s2 - s键长为242 pm的Ψ -四面体SbS3-3阴离子以立方面为中心排列，其中三种晶体结构不同的a +阳离子占据了四面体和八面体的空隙，总体上表现为扭曲的八面体硫配位。利用FP-LAPW能带结构计算方法研究了其化学键和立体化学活性孤电子对的特征。以Sb2O3、CsOH和单质硫为悬浮液，制备了锑(V)盐Cs3SbS4·H2O一水晶体。Cs3SbS4·H2O结晶为新的结构类型(单斜晶型，空间群P21/c， a = 987:17(10), b = 994:83(7), c = 1600:46（14) pm, β = 126:895(8)°，Z = 4, R1 = 0:0234）。正如预期的那样，几乎理想的四面体阴离子SbS3-4中的Sb-S距离（233.1 - 234.7 pm）比锑酸盐（III）中的Sb-S距离短得多，但与无水硫锑酸盐(V) Cs3SbS4中的键长相匹配。由于锑酸盐（III）中具有类似fcc的阴离子排列和Sb的立体化学活性孤电子对，整个系列化合物A3SbIII，VS3/4呈现出统一的结构关系，并用晶体群-亚群关系对其进行了分析。（K=Rb=Cs）3SbS3和Cs3SbS4·H2O的合成、晶体结构和化学键
The new sulfido antimonates(III) (Rb=Cs)3SbS3 were prepared from the alkali metal sulfides Rb2S=Cs2S2 and elemental antimony and sulfur or Sb2S3 at reaction temperatures of about 700 °C. The known isotypic potassium compound was similarily synthesized from the elements. The structures of the light-yellow crystals were refined using single-crystal X-ray data. Both compounds are isotypic to the respective Na salt forming the Na3AsS3 structure type (cubic, space group P213, K/Rb/Cs: a = 947:21(7)=982:28(5)=1025:92(5) pm, Z = 4, R1 = 0:0159=0:0560=0:0582). The Ψ - tetrahedral SbS3-3 anions with Sb-S bond lengths of 242 pm are arranged in a cubic face centered packing, in which the three crystallographically different A+ cations occupy the tetrahedral and octahedral voids, overall exhibiting a distorted octahedral sulfur coordination. The chemical bonding and the characteristics of the stereochemically active lone electron pair have been investigated by means of FP-LAPW band structure calculations. Needle-shaped crystals of the monohydrate of the antimony(V) salt Cs3SbS4 · H2O were obtained from a suspension of Sb2O3, CsOH and elemental sulfur. Cs3SbS4 · H2O crystallizes in a new structure type (monoclinic, space group P21/c, a = 987:17(10), b = 994:83(7), c = 1600:46(14) pm, β = 126:895(8)°, Z = 4, R1 = 0:0234). As expected, the Sb-S distances (233.1 - 234.7 pm) in the nearly ideally tetrahedral anion SbS3-4 are considerably shorter than in the antimonates(III) but match the bond lengths in the anhydrous sulfido antimonate(V) Cs3SbS4. Due to their similar fcc-like anion packing and the stereochemically active lone electron pair of Sb in the antimonates(III), the whole series of compounds A3SbIII,VS3/4 shows a uniform structure relation, which is elucidated using crystallographic group-subgroup relations Graphical Abstract Neue Sulfido-Antimonate der schweren Alkalimetalle: Synthese, Kristallstruktur und chemische Bindung von (K=Rb=Cs)3SbS3 und Cs3SbS4 · H2O / New Sulfido Antimonates of the Heavy Alkali Metals: Synthesis, Crystal Structure and Chemical Bonding of (K=Rb=Cs)3SbS3 and Cs3SbS4 · H2O