New strontium polysulfides, SrS3, and Sr2(OH)2S4.10H2O, obtained by the high-pressure treatment of a Sr-S mixture.
New strontium polysulfides, SrS3, and Sr2(OH)2S4.10H2O, obtained by the high-pressure treatment of a Sr-S mixture.
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DOI：
10.1021/ic0494612
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发表时间：
2004-09
影响因子：
4.6
通讯作者：
H. Fukuoka;Rimiko Suga;K. Komaguchi;S. Yamanaka;M. Shiotani
中科院分区：
文献类型：
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作者：
H. Fukuoka;Rimiko Suga;K. Komaguchi;S. Yamanaka;M. Shiotani
通过SrS和S在1200℃、5 GPa压力下以Sr:S = 1:5的原子比反应，得到了SrS(3)的新多晶型。它结晶为四方晶胞，a = 6.708(1) A，c = 3.942(1) A，V = 177.36(6) A(3)。它与BaS(3) 是同型的，并且含有S3(2-) 多硫离子。由高压合成获得的产物含有无定形组分。它高度潮解并形成淡黄色溶液。一种新的层状多硫化物Sr(2)(OH)(2)S(4).10H(2)O在溶液中结晶。该硫化物属于三斜空间群P（No.2），晶格常数为a = 5.9107（5）A，b = 7.8682（6）A，c = 9.4134（6）A，α = 75.639（6）度，β = 73.824（3）度，gamma = 71.639（3）度，V = 392.83(5) A(3)，且 Z = 1。每个 Sr 离子与一个 OH 配体和八个 H(2)O 配体配位。八个中的六个H(2)O配体是桥连配体，形成二维[Sr(2)(OH)(2)(H(2)O)(10)(2+)](无穷大)阳离子层，S4(2-)四多硫离子位于其间。 S4(2-)阴离子具有二面角为180.0度的共面构型。从改变S4(2-)二面角的从头MO计算的角度讨论了具有不同构象的S4(2-)阴离子的稳定性。
A new polymorph of SrS(3) was obtained by a reaction of SrS and S with an atomic ratio of Sr:S = 1:5 under a pressure of 5 GPa at 1200 degrees C. It crystallized in a tetragonal unit cell with a = 6.708(1) A, c = 3.942(1) A, and V = 177.36(6) A(3). It was isotypic with BaS(3), and contained S3(2-) polysulfide ions. The product obtained from the high-pressure synthesis contained an amorphous component. It was highly deliquescent and formed a yellowish solution. A new layered polysulfide, Sr(2)(OH)(2)S(4).10H(2)O, crystallized in the solution. The sulfide belonged to a triclinic space group of P (No. 2) with lattice constants of a = 5.9107(5) A, b = 7.8682(6) A, c = 9.4134(6) A, alpha = 75.639(6) degrees, beta = 73.824(3) degrees, gamma = 71.639(3) degrees, V = 392.83(5) A(3), and Z = 1. Each Sr ion was coordinated with one OH ligand and eight H(2)O ligands. Six H(2)O ligands out of the eight were bridging ligands to form two-dimensional [Sr(2)(OH)(2)(H(2)O)(10)(2+)]( infinity ) cationic layers, between which S4(2-) tetrapolysulfide ions were situated. The S4(2-) anion had a coplanar configuration with a dihedral angle of 180.0 degrees. The stability of S4(2-) anions having different conformations was discussed from a viewpoint of ab initio MO calculations on changing the dihedral angles of S4(2-).