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1.
Hung LI  Wang SL  Kao HM  Lii KH 《Inorganic chemistry》2003,42(13):4057-4061
A new indium(III) silicate, K(2)In(OH)(Si(4)O(10)), has been synthesized by a high-temperature, high-pressure hydrothermal method. It crystallizes in the monoclinic space group P2(1)/m (No. 11) with a = 11.410(1) A, b = 8.373(1) A, c = 11.611(1) A, beta = 112.201(2) degrees, and Z = 4. The structure, which is analogous to that of K(2)CuSi(4)O(10), consists of unbranched vierer 4-fold chains of corner-sharing SiO(4) tetrahedra running along the b axis linked together via corner sharing by chains of trans-corner-sharing InO(4)(OH)(2) octahedra to form a 3-D framework which delimits 8-ring and 6-ring channels to accommodate K(+) cations. The presence of hydroxyl groups is confirmed by IR spectroscopy. The (29)Si MAS NMR exhibits four resonances at -88.6, -90.1, -97.4, and -98.2 ppm corresponding to four distinct crystallographic Si sites. A (1)H --> (29)Si CP/MAS NMR experiment was performed to assign the four resonances.  相似文献   

2.
A novel indium silicate, Rb3In(H2O)Si5O13, has been synthesized using a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction. The structure consists of five-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to four adjacent five-membered rings to form a 3D silicate framework that belongs to the CdSO4 topological type. The InO6 octahedron shares five of its corners with five different SiO4 tetrahedra to form a 3D frame-work that delimits two types of channels to accommodate the rubidium cations. The sixth corner of InO6 is coordinated H2O. The structure is related to that of the titanium silicate ETS-10, and these are the only two metal silicates that have the CdSO4-topological-type structure. In addition, the crystal of Rb3In(H2O)Si5O13 shows an intense second harmonic generation signal. Crystal data: H2Rb3InSi5O14, monoclinic, space group Cc (No. 9), a = 9.0697(5) A, b = 11.5456(6) A, c = 13.9266(8) A, beta = 102.300(1) degrees, V = 1424.8(1) A3, and Z = 4.  相似文献   

3.
Chen CS  Chiang RK  Kao HM  Lii KH 《Inorganic chemistry》2005,44(11):3914-3918
A new uranium(VI) silicate, Cs2(UO2)(Si2O6), has been synthesized by a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction and solid-state NMR spectroscopy. It crystallizes in the orthorhombic space group Ibca (No. 73) with a = 15.137(1) A, b = 15.295(1) A, c = 16.401(1) A, and Z = 16. Its structure consists of corrugated achter single chains of silicate tetrahedra extending along the c axis linked together via corner-sharing by UO6 tetragonal bipyramids to form a 3-D framework which delimits 8- and 6-ring channels. The Cs+ cations are located in the channels or at sites between channels. The 29Si and 133Cs MAS NMR spectra are consistent with the crystal structure as determined from X-ray diffraction, and the resonances in the spectra are assigned. Variable-temperature in situ powder X-ray diffraction study of the hydrate Cs2(UO2)(Si2O6) x 0.5H2O indicates that the framework structure is stable up to 800 degrees C and transforms to the structure of the title compound at 900 degrees C. A comparison of related uranyl silicate structures is made.  相似文献   

4.
Hung LI  Wang SL  Chen YH  Lii KH 《Inorganic chemistry》2006,45(5):2100-2103
A new cobalt-indium silicate, Rb6(InCo)2(Si9O26), has been synthesized via a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction. It crystallizes in the noncentrosymmetric orthorhombic space group Aba2 (No. 41) with a = 20.779(1) A, b = 12.0944(6) A, c = 10.7761(5) A, V =2708.1(2) A(3), and Z = 4. The structure consists of 20-membered-ring silicate single layers of corner-sharing SiO4 tetrahedra interconnected by dimers of edge-sharing CoO4 tetrahedra and InO6 octahedra into a 3D framework. The Si:O ratio for the title compound is the lowest among the known single-layer silicates. Magnetic susceptibility confirms the divalent state of the cobalt ion. The powder sample has a second-harmonic-generation signal, confirming the absence of a center of symmetry in the structure.  相似文献   

5.
Li CY  Hsieh CY  Lin HM  Kao HM  Lii KH 《Inorganic chemistry》2002,41(16):4206-4210
A new vanadium(IV) silicate, Rb(2)(VO)(Si(4)O(10)).xH(2)O (x approximately 0.1), has been synthesized by a high-temperature, high-pressure hydrothermal method. It crystallizes in the tetragonal space group I4(1)md (No. 109) with a = 12.2225(7) A, c = 7.7948(6) A, and Z = 4. The structure consists of spiral chains of corner-sharing SiO(4) tetrahedra linked to neighboring chains via corner sharing to form a 3-D silicate framework which delimits channels to accommodate the VO(2+) groups. The Rb(+) ions are located in the cavities within the silicate framework. Magnetic susceptibility confirms the valence of vanadium. A partially occupied lattice water site is confirmed by IR and solid state (1)H NMR spectroscopy. The structure of the title compound is considerably different from those of the synthetic silicate K(2)(VO)(Si(4)O(10)).H(2)O and the two polymorphs of the natural mineral Ca(VO)(Si(4)O(10)).4H(2)O, although they have identical framework stoichiometry.  相似文献   

6.
A new uranium(VI) silicate, K5(UO2)2[Si4O12(OH)], has been synthesized by a high-temperature, high-pressure hydrothermal method. It crystallizes in the orthorhombic space group Pbcm (No. 57) with a = 13.1274(7) A, b = 12.2635(7) A, c = 22.233(1) A, and Z= 8. Its structure consists of unbranched chains of four silicate tetrahedra extending along the b axis linked together via corner-sharing by UO6 tetragonal bipyramids to form a 3-D framework, which delimits intersecting channels along the c and b axes to accommodate K+ cations. A hydrogen atom is bonded to a terminal oxygen of a terminal silicate in the oligosilicate anion. Adjacent chains are linked along the b axis by hydrogen bonds. The sample shows a resonance at 14.7 ppm the 1H MAS NMR spectrum, which is assigned to the SiO...HOSi hydrogen bond. A comparison of uranyl silicate structures is made.  相似文献   

7.
在含有HF的体系中, 用乙二胺作模板剂, 通过水热方法合成了一个新的三维亚磷酸铟[In4(HPO3)7(H2O)3](NH3CH2CH2NH3)·(H2O), 并对其进行了红外光谱、热重、ICP和CHN元素分析等表征. 单晶X射线衍射分析结果表明, 该化合物属于三方晶系, P3空间群, 晶胞参数a=1.37883(7) nm, c=0.93450(9) nm, V=1.53862(2) nm3, Z=2, Dc=2.489 Mg/m3, 最终一致性因子R1[I >2σ(I)]=0.0526, wR2[I>2σ(I)]=0.1328, GOF=1.082. 其结构中的InO6八面体、InO5(H2O)八面体和HPO3假四面体通过O原子共顶点连接, 分别沿a, b轴方向形成含有十二元环的交叉孔道, 客体水分子和双质子化的乙二胺分子存在于孔道中.  相似文献   

8.
Liu HK  Chang WJ  Lii KH 《Inorganic chemistry》2011,50(22):11773-11776
A new uranium(VI) silicate, Cs(2)UO(2)Si(10)O(22), has been synthesized by a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction, luminescence, and solid state NMR spectroscopy. It crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 12.2506(4) ?, b = 8.0518(3) ?, c = 23.3796(8) ?, β = 90.011(2)°, and Z = 4. Its structure consists of silicate double layers in the ab plane which are connected by UO(6) tetragonal bipyramids via four equatorial oxygen atoms to form a 3D framework with nine-ring channels parallel to the b axis where the Cs(+) cations are located. The photoluminescence emission spectrum at room temperature consists of one broad structured band which is typical of uranyl. The (29)Si MAS NMR spectrum is consistent with the crystal structure as determined from X-ray diffraction, and the resonances in the spectrum are assigned. A comparison of related uranyl silicate structures is made.  相似文献   

9.
Zhao X  Li J  Chen P  Li Y  Chu Q  Liu X  Yu J  Xu R 《Inorganic chemistry》2010,49(21):9833-9838
Three new lanthanide silicates K(1.25)Gd(1.25)Si(2.5)O(7.5) (denoted as GdSiO-CJ7), Cs(3)TbSi(8)O(19)·2H(2)O (denoted as TbSiO-CJ8), and Cs(3)DySi(6)O(15) (denoted as DySiO-CJ9) were synthesized by using a high-temperature and high-pressure hydrothermal method. Their structures determined by single-crystal X-ray diffraction revealed anionic silicate chain, layer and framework, which are further connected with LnO(n) polyhedra to form novel lanthanide silicate frameworks. The structure of GdSiO-CJ7 consists of unbranched silicate chains [Si(5)O(15)](10-) extending along the b axis, which are linked together by edge-sharing linked GdO(6) and GdO(8) chains along the c axis to form a 3-D framework with two types of 10-ring channels along the [010] and [001] directions, respectively. The structure of TbSiO-CJ8 consists of double 4,8-net sheets [Si(8)O(19)](6-) built up from SiO(4) tetrahedra, which are linked together via TbO(6) octahedra to form a 3-D framework with 8-ring channels along the [100] and [010] directions. The structure of DySiO-CJ9 is based on a 3-D silicate framework [Si(6)O(15)](6-) with 6-rings, where DyO(6) octahedra are located between two adjacent 6-rings and connected with six Si atoms via O atoms. The photoluminescence photoluminescence properties of TbSiO-CJ8 and EuSiO-CJ8 were investigated.  相似文献   

10.
Wang GM  Li JH  Li ZX  Huang HL  Xue SY  Liu HL 《Inorganic chemistry》2008,47(4):1270-1272
QD-3, a novel aluminoborate (TETA) 2[Al 2B 10 O 20].0.25H 2O (TETA = triethylenetetramine), has been solvothermally synthesized and characterized by IR, thermogravimetric analysis, power X-ray diffraction, elemental analysis, and single-crystal X-ray diffraction. This compound crystallizes in the orthorhombic system, space group Pna2 1 (No. 33), a = 25.9174(2) A, b = 7.4028(5) A, c = 17.013(4) A, V = 3264.2(2) A (3), and Z = 4. Its structure consists of AlO 4 tetrahedra and B 5O 10 clusters, which are interconnected and form a three-dimensional framework with large 11-, 12-, and 14-ring channels.  相似文献   

11.
Lii KH  Wang SL  Liao FL 《Inorganic chemistry》2004,43(8):2499-2502
Cs(2)Pd(3)(P(2)O(7))(2) (1) and Cs(2)Pd(3)(As(2)O(7))(2) (2) have been synthesized by molten flux reactions and characterized by single-crystal X-ray diffraction. The structure of 1 consists of discrete Pd(II)O(4) squares which are linked by P(2)O(7) groups via corner-sharing to generate a 3D framework containing 12-ring channels in which Cs(+) cations are located. Compound 2 adopts a 2D layer structure with the interlayer space filled with Cs(+) cations. Within a layer there are PdO(4) squares and As(2)O(7) groups fused together via corner-sharing. Adjacent layers are stacked such that strings of Pd atoms are formed. The PdO(4) squares show eclipsed and staggered stacks with alternate short and long Pd...Pd distances. The two compounds adopt considerably different structures although they have the same general formula: Cs(2)Pd(3)(X(2)O(7))(2). Compound 2 is the first palladium arsenate reported. Crystal data for 1: orthorhombic, space group Cmc2(1) (No. 36), a = 7.6061(4) A, b = 14.2820(7) A, c = 14.1840(7) A, and Z = 4. Crystal data for 2: tetragonal, space group P4/n (No. 85), a = 16.251(1) A, c = 5.9681(5) A, and Z = 4.  相似文献   

12.
Two Np(5+) silicates, Li(6)(NpO(2))(4)(H(2)Si(2)O(7))(HSiO(4))(2)(H(2)O)(4) (LiNpSi1) and K(3)(NpO(2))(3)(SiO(3)OH)(2) (KNpSi1), were synthesized by hydrothermal methods. The crystal structures were determined using direct methods and refined on the basis of F(2) for all unique data collected with Mo Kalpha radation and an APEX II CCD detector. LiNpSi1 crystallizes in orthorhombic space group Pnma with a =13.189(6) A, b = 7.917(3) A, c = 10.708(5) A, V = 1118.1(8) A3, and Z = 2. KNpSi1 is hexagonal, P62m, a = 9.734(1) A, c = 3.8817(7) A, V = 318.50(8) A3, and Z = 1. LiNpSi1 contains chains of edge-sharing neptunyl pentagonal bipyramids linked into two-dimensional sheets through direct linkages between the neptunyl polyhedra and the vertex sharing of the silicate tetrahedra. The structure contains both sorosilicate and nesosilicate units, resulting in a new complex neptunyl silicate sheet. KNpSi1 contains edge-sharing neptunyl square bipyramids linked into a framework structure through the sharing of vertices with the silicate tetrahedra. The neptunyl silicate framework contains channels approximately 6.0 A in diameter. These structures exhibit significant departures from other reported Np(5+) and U(6+) compounds and represent the first reported Np(5+) silicate structures.  相似文献   

13.
The open-framework uranium fluorosilicate [(CH3)4N][(C5H5NH)0.8((CH3)3NH)0.2]U2Si9O23F4 (USH-8) has been synthesized hydrothermally by using tetramethylammonium hydroxide and pyridine-HF. The compound has a framework composition U2Si9O23F4 based on silicate double layers that are linked by chains of UO3F4 pentagonal bipyramids. The framework has 12-ring channels along [010] and 7-ring channels along [100]. The [010] 12-ring channels have a calabash-shape with the middle part partially blocked by the uranyl oxygen atoms. The narrow side of the 12-ring channels is occupied by well-ordered TMA cations while the wide side is occupied by disordered pyridinium and trimethylammonium cations.  相似文献   

14.
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.  相似文献   

15.
Yang M  Yu J  Di J  Li J  Chen P  Fang Q  Chen Y  Xu R 《Inorganic chemistry》2006,45(9):3588-3593
Three new open-framework transition-metal borophosphates Na5(H3O){M(II)3[B3O3(OH)]3(PO4)6}.2H2O (M(II) = Mn, Co, Ni) (denoted as MBPO-CJ25) have been synthesized under mild hydrothermal conditions. Single-crystal X-ray diffraction analyses reveal that the three compounds possess isostructural three-dimensional (3D) open frameworks with one-dimensional 12-ring channels along the [001] direction. Notably, the structure can also be viewed as composed of metal phosphate layers [M(II)(PO4)2]4- with Kagomé topology, which are further connected by [B3O7(OH)] triborates, giving rise to a 3D open framework. The guest water molecules locate in the 12-ring channels. Partial Na+ ions reside in the 10-ring side pockets within the wall of the 12-ring channels, and the other Na+ ions and protonated water molecules locate in the 6-ring windows delimited by MO6 and PO4 polyhedra to compensate for the negative charges of the anionic framework. These compounds show a high thermal stability and are stable upon calcinations at ca. 500 degrees C. Ionic conductivities, due to the motion of Na+ ions, are measured for these three compounds. They have similar activation energies of 1.13-1.25 eV and conductivities of 2.7 x 10(-7)-9.9 x 10(-7) S cm(-1) at 300 degrees C. Magnetic measurements reveal that there are very weak antiferromagnetic interactions among the metal centers of the three compounds. Crystal data: MnBPO-CJ25, hexagonal, P6(3)/m (No. 176), a = 11.9683(5) A, c = 12.1303(6) A, and Z = 2; CoBPO-CJ25, hexagonal, P6(3)/m (No. 176), a = 11.7691(15) A, c = 12.112(2) A, and Z = 2; NiBPO-CJ25, hexagonal, P6(3)/m (No. 176), a = 11.7171(5) A, c = 12.0759(7) A, and Z = 2.  相似文献   

16.
The reaction of UO(2)(NO(3))(2).6H(2)O with Cs(2)CO(3) or CsCl, H(3)PO(4), and Ga(2)O(3) under mild hydrothermal conditions results in the formation of Cs(4)[(UO(2))(2)(GaOH)(2)(PO(4))(4)].H(2)O (UGaP-1) or Cs[UO(2)Ga(PO(4))(2)] (UGaP-2). The structure of UGaP-1 was solved from a twinned crystal revealing a three-dimensional framework structure consisting of one-dimensional (1)(infinity)[Ga(OH)(PO(4))(2)](4-) chains composed of corner-sharing GaO(6) octahedra and bridging PO(4) tetrahedra that extend along the c axis. The phosphate anions bind the UO(2)(2+) cations to form UO(7) pentagonal bipyramids. The UO(7) moieties edge-share to create dimers that link the gallium phosphate substructure into a three-dimensional (3)(infinity)[(UO(2))(2)(GaOH)(2)(PO(4))(4)](4-) anionic lattice that has intersecting channels running down the b and c axes. Cs(+) cations and water molecules occupy these channels. The structure of UGaP-2 is also three-dimensional and contains one-dimensional (1)(infinity)[Ga(PO(4))(2)](3-) gallium phosphate chains that extend down the a axis. These chains are formed from fused eight-membered rings of corner-sharing GaO(4) and PO(4) tetrahedra. The chains are in turn linked together into a three-dimensional (3)(infinity)[UO(2)Ga(PO(4))(2)](1-) framework by edge-sharing UO(7) dimers as occurs in UGaP-1. There are channels that run down the a and b axes through the framework. These channels contain the Cs(+) cations. Ion-exchange studies indicate that the Cs(+) cations in UGaP-1 and UGaP-2 can be exchanged for Ca(2+) and Ba(2+). Crystallographic data: UGaP-1, monoclinic, space group P2(1)/c, a = 18.872(1), b = 9.5105(7), c = 14.007(1) A, beta = 109.65(3)(o) , Z = 4 (T = 295 K); UGaP-2, triclinic, space group P, a = 7.7765(6), b = 8.5043(7), c = 8.9115(7) A, alpha = 66.642(1)(o), beta = 70.563(1)(o), gamma = 84.003(2)(o), Z = 2 (T = 193 K).  相似文献   

17.
Two new quaternary mixed metal oxide materials--InVTe(2)O(8) and InVSe(2)O(8)--have been synthesized, as crystals and pure bulk powders by standard solid-state reactions using In(2)O(3), V(2)O(5), and TeO(2) (or SeO(2)) as reagents. The crystal structures of the reported materials were determined using single-crystal X-ray diffraction. InVTe(2)O(8) crystallizes in the monoclinic centrosymmetric space group P2(1)/n (No. 14), with unit-cell parameters of a = 7.8967(16) ?, b = 5.1388(10) ?, c = 16.711(3) ?, β = 94.22(3)°, and Z = 4, and InVSe(2)O(8) crystallizes in the noncentrosymmetric space group Pm (No. 6) with unit-cell parameters of a = 4.6348(9) ?, b = 6.9111(14) ?, c = 10.507(2) ?, β = 97.77(3)°, and Z = 2. While the centrosymmetric InVTe(2)O(8) shows a two-dimensional (2D) layered structure composed of InO(6) octahedra, VO(4) tetrahedra, and TeO(4) polyhedra, the noncentrosymmetric InVSe(2)O(8) exhibits a three-dimensional (3D) framework structure with distorted InO(6) octahedra, VO(5) square pyramids, and SeO(3) polyhedra. Powder second-harmonic generation (SHG) measurements on InVSe(2)O(8), using 1064-nm radiation, indicate that the material has a SHG efficiency ~30 times that of α-SiO(2). Additional SHG measurements reveal that the material is not phase-matchable (Type 1). Infrared, ultraviolet-visible light (UV-vis) diffuse reflectance, and thermogravimetric analyses for the two compounds are also presented, as are dipole moment calculations.  相似文献   

18.
Sheu CY  Lee SF  Lii KH 《Inorganic chemistry》2006,45(5):1891-1893
Two new iron(III) oxalatophosphates, Cs2Fe(C2O4)(0.5)(HPO4)2 (1) and CsFe(C2O4)(0.5)(H2PO4)(HPO4) (2), have been synthesized by using a low melting point eutectic mixture of choline chloride and malonic acid as a solvent and characterized by single-crystal X-ray diffraction and magnetic susceptibility. Crystal data are as follows: compound 1, monoclinic, P2(1)/c (No. 14), a = 8.5085(4) A, b = 12.7251(6) A, c = 9.8961(4) A, beta = 107.117(1) degrees , V = 1024.01(8) A(3), Z = 4, and R(1) = 0.0264; compound 2, monoclinic, P2(1)/n (No. 14), a = 8.0038(3) A, b = 10.2923(3) A, c = 11.4755(4) A, beta = 100.507(1) degrees , V = 929.47(5) A(3), Z = 4, and R(1) = 0.0311. The structure of 1 comprises FeO6 octahedra connected by HPO4(2-) tetrahedra and bisbidentate oxalate anions to form a 3D framework containing intersecting 12-ring channels, with the charge-compensating Cs+ cations being located at the intersections of these channels. The structure of 2 consists of 2D layers of octahedral FeO6, tetrahedral H2PO4- and HPO4(2-) moieties, and bisbidentate oxalate ligands with the Cs+ cations between the layers. They are the first examples for the use of ionic liquid as a solvent in the synthesis of metal oxalatophosphates.  相似文献   

19.
用熔盐法合成了新型硅酸铀K4(UO2),Si8O22,并用单晶X射线衍射确定结构.结果表明,化合物由UO6 双四角椎及硅酸根四面体构成的(Si8O22)12-单元组成,其中(Si8O22)12-单元的结构形态是最新发现的.29Si MAS NMR测定结果与晶体结构相吻合,而光致发光光谱证实了六价铀的存在.K(UO2),...  相似文献   

20.
The first organically templated 3D borogermanate with a novel zeolite-type topology, (C4N3H15)[(BO2)2(GeO2)4] FJ-17, has been solvothermally synthesized and characterized by IR spectroscopy, powder X-ray diffraction (PXRD), TGA, and single-crystal X-ray diffraction. The compound crystallized in the monoclinic space group P2(1)/c with a = 6.967(1) A, b = 10.500(1) A, c = 20.501(1) A, beta = 90.500(3) degrees , V = 1499.68(8) A3, and Z = 4. The framework topology of this compound is the previously unknown topology with the vertex symbols 3.4.3.9.3.8(2) (vertex 1), 3.8.3.4.6(2).9(2) (vertex 2), 3.8(2).4.6(2).6(2).8 (vertex 3), 4.8.4.8.8(3).12 (vertex 4), 4.8.4.8.8(2).12 (vertex 5), and 3.8.4.6(2).6.8(2) (vertex 6). The structure is constructed from Ge8O24 and B2O7 clusters. The Ge8O24 cluster contains eight GeO4 tetrahedra that share vertices; the B2O7 unit is composed of two BO4 tetrahedra sharing a vertex. The cyclic Ge8O24 clusters connect to each other through vertices to form a 2D layer with 8,12-nets. The adjacent layers are further linked by the dimeric B2O7 cluster units, resulting in a 3D framework with 12- and 8-ring channels along the a and b axes, respectively. In addition, there is a unique B2GeO9 3-ring in the structure.  相似文献   

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