水热法合成了新结构类型化合物CsIn[PO3(OH)]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:Mr=439.69,mP56,a=0.53286(6)nm,b=0.91653(7)nm,c=1.47839(14)nm,β=93.849(9)°,V=0.7204(1)nm3,Z=4,Dx=4.054g·cm-3,μ=8.713mm-1,F(000)=800,R1=0.0325,wR2=0.0874。在该化合物中,2个InO6八面体和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(OH)]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(OH)]2与之同构。A cesium indium hydrated phosphate, CsIn2, was synthesized under mild hydrothermal conditions, and the crystal structures were characterized by single crystal X-ray diffraction method. CsIn2 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 Na2In24·H2O with the similar stoichiometry. The topological construction of the title structure can be considered as an augmented 6,3-net. RbIn2 is isotypic to the Cs compound. CSD: 391266.国家自然科学基金资助项目(No.50332050);; 国家杰出青年基金资助项目(No.20025101);; 国家科技部“863”计划(No.2002AA324070);; 上海市科委光科技项目(No.D11161015)资
