具有新结构类型的化合物Csln[PO3(OH)]2的合成与结构

水热法合成了新结构类型化合物CsIn[P03(0H)]2,并通过单晶X-射线衍射表征结构.标题化合物空间群为P121/c1(No.14),晶体学参数为:M=439.69,mP56,a=0.532 86(6)nm,b=0.91653(7)nm,c=1.478 39(14)nm,β=93.849(9).,V=0.7204(1)nm3,Z=4,Dx=4.054 g·cm-3,μ=8.713 mm-1,F(000)=800,R1= 0.0325,wR2=0.0874.在该化合物中,2个In06八面体和4个PO4四面体形成交连的六元环柱,并沿a轴方向形成近六方密堆积并连接成Cs+离子占据的十二元环结构隧道,六元环和十二元环连接构筑了三维网络结构.与类似化学计量比化合物Na2In2[PO3(0H)]4·H2O比较,标题化合物中十二元环的形成明显取决于隧道阳离子的大小,其拓扑构造可看作扩展的6,3-网格连接,化合物RbIn[PO3(0H)]2与之同构.

New Indium(Ⅲ)Phosphate CsIn[PO3(OH)]2 with a New Type of Structure

A cesium indium hydrated phosphate,Csln[PO3(OH)]2,was synthesized under mild hydrothermal conditions,and the crystal structures were characterized by single crystal X-ray diffraction method.Csln[PO3(OH)]2 has a new type of crystal structure.Crystallographic data are as following:Mr=439.69,monoclinic,mP56,P1 21/c 1(No.14),a=0.532 86(6)nm,b=0.916 53(7)nm,c=1.478 39(14)nm,β=93.849(9)°,V=0.720 4(1)nm3,Z=4,Dx=4.054 g·cm-3,μ=8.713 mm-1,F(000)=800,R1=0.032 5,wR2=0.087 4 for 116 variables and 1 502 contributing unique reflections.The structure is characterized by 6-membered column with cross-section formed by two InO6 octahedra and four PO4 tetrahedra. The condensation of the column forms an almost hexagonal close-packing array along a axis, resulting in close packing of 12-membered-ring channels occupied by Cs+ cations. The connections of the columns and channels result in a three-dimensional network structure. The formation of the 12-membered ring in these structures seems clearly governed by the cation size by comparing to Na2In2[PO3(OH)]4·H2O with the similar stoichiometry. The topological construction of the title structure can be considered as an augmented 6,3-net.RbIn [PO3(OH)]2 is isotypic to the Cs compound.CSD: 391266.