Lee Eunsil, Lee Yonghee, Yun Hoseop
Division of Energy Systems Research and Department of Chemistry, Ajou University, Suwon 443-749, Republic of Korea.
Acta Crystallogr Sect E Struct Rep Online. 2010 Dec 24;67(Pt 1):i4. doi: 10.1107/S1600536810052724.
The quaternary thio-phosphate, Cs(0.49)NbPS(6), caesium hexa-thio-niobiophosphate(V), has been synthesized by the reactive halide flux method. The title compound is isotypic with Rb(0.46)TaPS(6) and is made up of a bicapped trigonal-biprismatic [Nb(2)S(12)] unit and a tetra-hedral [PS(4)] group. The [Nb(2)S(12)] units linked by the [PS(4)] tetra-hedra form infinite chains, yielding a three-dimensional network with rather large van der Waals gaps along the c axis in which the disordered Cs(+) ions reside. The electrons released by the Cs atoms are transferred to the pairwise niobium metal site and there are substantial inter-metallic Nb-Nb bonding inter-actions. This leads to a significant decrease of the inter-metallic distance in the title compound compared to that in TaPS(6). The classical charge balance of the title compound may be represented as Cs(+)[Nb(4.51+)][P(5+)]S(2-)[S(2) (2-)].
通过反应性卤化物助熔剂法合成了四元硫代磷酸盐Cs(0.49)NbPS(6)，即六硫代铌(V)酸铯。标题化合物与Rb(0.46)TaPS(6)同型，由一个双帽三角双棱柱形的[Nb(2)S(12)]单元和一个四面体[PS(4)]基团组成。由[PS(4)]四面体连接的[Nb(2)S(12)]单元形成无限链，产生一个沿c轴具有相当大范德华间隙的三维网络，无序的Cs(+)离子位于其中。Cs原子释放的电子转移到成对的铌金属位点，并且存在大量的金属间Nb-Nb键相互作用。这导致标题化合物中的金属间距离与TaPS(6)相比显著减小。标题化合物的经典电荷平衡可表示为Cs(+)[Nb(4.51+)][P(5+)]S(2 -)[S(2 2 -)]。
