Na2[(VO)2(HPO4)2C2O4].2H2O: crystal structure determination from combined powder diffraction and solid-state NMR

The vanadyl oxalatophosphate Na2[(VO)2(HPO4)2C2O4].2H2O has been synthesized by hydrothermal treatment. Its structure has been determined and refined by combining X-ray powder diffraction and solid-state NMR techniques. It crystallizes with monoclinic symmetry in space group P2(1), a = 6.3534(1) A, b = 17.1614(3) A, c = 6.5632(1) A, beta = 106.597(1) degrees . The structure is related to that of (NH4)2[(VO)2(HPO4)2C2O4].5H2O, which was previously reported. The vanadium phosphate framework consists of infinite [(VO)(HPO4)] chains of corner-sharing vanadium octahedra and hydrogenophosphate tetrahedra. The oxalate groups ensure the connection between the chains to form a 2D structure. The sodium ions and the water molecules are located between the anionic [(VO)2(HPO4)2C2O4]2- layers. The thermal decomposition has been studied in situ by temperature-dependent X-ray diffraction and thermogravimetry. It takes place in three stages, where the first two correspond to water removal and the last to the decomposition of the oxalate group and water elimination, leading to the final product NaVOPO4.     

Preparation, structure, and properties of tetranuclear vanadium(III) and (IV) complexes bridged by diphenyl phosphate or phosphate

Three novel tetranuclear vanadium(III) or (IV) complexes bridged by diphenyl phosphate or phosphate were prepared and their structures characterized by X-ray crystallography. The novel complexes are [{V(III)(2)(μ-hpnbpda)}(2){μ-(C(6)H(5)O)(2)PO(2)}(2)(μ-O)(2)]·6CH(3)OH (1), [{V(III)(2)(μ-tphpn)(μ-η(3)-HPO(4))}(2)(μ-η(4)-PO(4))](ClO(4))(3)·4.5H(2)O (2), and [{(V(IV)O)(2)(μ-tphpn)}(2)(μ-η(4)-PO(4))](ClO(4))(3)·H(2)O (3), where hpnbpda and tphpn are alkoxo-bridging dinucleating ligands. H(3)hpnbpda represents 2-hydroxypropane-1,3-diamino-N,N'-bis(2-pyridylmethyl)-N,N'-diacetic acid, and Htphpn represents N,N,N',N'-tetrakis(2-pyridylmethyl)-2-hydroxy-1,3-propanediamine. A dinuclear vanadium(IV) complex without a phosphate bridge, [(VO)(2)(μ-tphpn)(H(2)O)(2)](ClO(4))(3)·2H(2)O (4), was also prepared and structurally characterized for comparison. The vanadium(III) center in 1 adopts a hexacoordinate structure while that in 2 adopts a heptacoordinate structure. In 1, the two dinuclear vanadium(III) units bridged by the alkoxo group of hpnbpda are further linked by two diphenylphosphato and two oxo groups, resulting in a dimer-of-dimers. In 2, the two vanadium(III) units bridged by tphpn are further bridged by three phosphate ions with two different coordination modes. Complex 2 is oxidized in aerobic solution to yield complex 3, in which two of the three phosphate groups in 2 are substituted by oxo groups.     

新型磷酸钒孔道结构化合物(H3NCH2CH2NH3)3- [ (VO)4(PO4)2 (HPO4)4]的水热 合成及结构表征

以有机分子乙二胺作为模板剂合成了新型磷酸钒孔道化合物(H3NCH2CH2NH3)3^-[(VO)4(PO4)2(HPO4)4,并通过X射线单晶衍射实验进行了结构表征,晶体学数据为：C2/c,a=1.8505(9)nm,b=0.7089(4)nm,c=2.3304(10)nm,β=96.43(3)°,V-3.038(3)nm^3,Z=8,R=0.067,Rw^b=0.1635,该化合物具有非常独特和规整的二维孔道骨架结构,进一步的晶体化学研究表明该化合物为一新的VPO物相。     

二维层状磷酸亚磷酸钒(Ⅳ)化合物[V2O2(OH)(HPO3)(HPO3)0.7(PO3OH)0.3].(C6N2H16)0.5的水热合成与结构表征

迄今, 在中温水热条件下已合成了大量具有空旷骨架结构的过渡金属磷酸盐微孔材料[1], 这类材料在非线性光学材料、磁性材料、超导材料及催化等诸多方面具有潜在的应用前景[2～5].     

Structural, magnetic, and ion-exchange properties of a new layered alkaline/alkaline earth iron phosphate: NaBaFe4(HPO4)3(PO4)3.H2O

A new mixed alkali/alkaline earth iron phosphate, NaBaFe4(HPO4)3.H2O, has been synthesized hydrothermally and structurally characterized by single-crystal X-ray diffraction, magnetic susceptibility, infrared spectroscopy, and thermogravimetric analysis. The title compound crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 9.287(2) A, b = 22.665(4) A, c = 8.966(3) A, beta = 91.82(2), and Z = 4. The compound has a 2-D framework structure constructed from layers, stacked along the [010] unit cell direction with Na+ and Ba2+ ions, and water molecules residing within the interlayer space. The anionic layers are composed from the assemblage of vertex shared FeO6 octahedra interconnected by PO4(3)- and HPO4(2)- tetrahedra. The layers are built from four unique FeO6 units linking through vertex shared oxygen atoms to form infinite zigzag chains that run parallel to the a axis. These chains form single layers that run infinitely in the c direction through the vertex sharing of PO4 groups.     

新型磷酸钒孔道结构化合物(H3NCH2CH2NH3)3- [ (VO)4(PO4)2 (HPO4)4]的水热 合成及结构表征

以有机分子乙二胺作为模板剂合成了新型磷酸钒孔道化合物(H3NCH2CH2NH3)3^-[(VO)4(PO4)2(HPO4)4,并通过X射线单晶衍射实验进行了结构表征,晶体学数据为：C2/c,a=1.8505(9)nm,b=0.7089(4)nm,c=2.3304(10)nm,β=96.43(3)°,V-3.038(3)nm^3,Z=8,R=0.067,Rw^b=0.1635,该化合物具有非常独特和规整的二维孔道骨架结构,进一步的晶体化学研究表明该化合物为一新的VPO物相。     

Ga(2,2'-bipy)(HPO(4))(H(2)PO(4)): first layered inorganic-organic hybrid gallium phosphate with a neutral framework

A novel gallium phosphate, Ga(2,2'-bipy)(HPO(4))(H(2)PO(4)) (denoted FJ-12; FJ = Fujian Institute of Research on the Structure of Matter), which is the first example of layered inorganic-organic hybrid gallium phosphate with neutral framework, has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. This compound crystallizes in the monoclinic system, space group P2(1)/c (No. 14), with a = 10.9443(9), b = 15.8253(13), and c = 8.4201(7) A, beta = 108.898(2) degrees, V = 1379.7(2) A(3), and Z = 4. The structure consists of HPO(4) and H(2)PO(4) tetrahedra and unusual GaO(4)N(2) octahedra which are linked through their vertexes forming an undulated sheetlike structure with 4.12-net. The adjacent layers are stably packed together and exhibit interesting 3-D supramolecular arrays pi-pi interactions of the 2,2'-bipy groups.     

A new two-dimensional molybdenum(V) nickel phosphate built up of [H18(Mo16O32)Ni16(PO4)26(OH)6(H2O)8]18- wheels

The new molybdenum(V) nickel phosphate Na(6)Ni(6)[(Mo(2)O(4))(8)Ni(16)(H(2)PO(4))(4)(HPO(4))(10)(PO(4))(12)(OH)(6)(H(2)O)(8)].66H(2)O (1) was synthesized hydrothermally. The structure (orthorhombic, space group Cccm; a = 23.999(4), b = 36.595(6), c = 20.445(4) A) was solved from single-crystal data. The framework structure of 1 consists of anionic inorganic sheets formed by the linkages of large polyoxomolybdate rings via nickel(II) octahedra. Charge-compensating sodium atoms are interleaved between the sheets. Magnetic studies of compound 1 revealed that among the 22 nickel(II) centers, 10 are interacting. The chi(M)T = f(T) curve can be fitted using the dinuclear expression appropriate to the HDVV isotropic exchange Hamiltonian H = -2JS(1).S(2), with S(1) = S(2) = 1 and J = -24.1 cm(-)(1), showing that nickel is antiferromagnetically coupled within Ni(2) pairs.     

Synthesis,structure, and magnetic properties of two new vanadocarboxylates with three-dimensional hybrid frameworks

(V(III)(OH))(2)[C(6)H(2)(CO(2))(4)].4H(2)O (labeled MIL-60) and V(III)(OH)[(2)(O(2)C)C(6)H(2)(COOH)(2)].H(2)O (labeled MIL-61) were hydrothermally synthesized from mixtures of VCl(3), 1,2,4,5-benzenetetracarboxylic acid, and water heated for 3 days at 473 K. The structure of MIL-60 was solved from single-crystal X-ray diffraction data in the triclinic centrosymmetric P1 (No. 2) space group with lattice parameters a = 6.3758(5) A, b = 6.8840(5) A, c = 9.0254(5) A, alpha = 69.010(2) degrees, beta = 85.197(2) degrees, gamma = 79.452(2) degrees, V = 363.53(5) A(3), and Z = 1. The structure of MIL-61 was ab initio determined from an X-ray powder diffraction pattern. MIL-61 crystallizes in the Pnma (No. 62) orthorhombic space group with lattice parameters a = 14.8860(1) A, b = 6.9164(1) A, c = 10.6669(2) A, V = 1098.23(3) A(3), and Z = 4. Both structures contain the same inorganic building block that consists of trans chains of V(III)O(4)(OH)(2) octahedra. The three-dimensional frameworks of MIL-60 and MIL-61 are constituted by the linkage of these chains via the organic molecules so delimiting the channels or cages where the water molecules are encapsulated. The magnetic behavior of these two phases is presented: MIL-60 is paramagnetic, and MIL-61 antiferromagnetically orders below T(N) = 55(5) K.     

Synthesis,crystal structure,and solid state NMR spectroscopy of NH(4)[(V(2)O(3))(2)(4,4'-bpy)(2)(H(2)PO(4))(PO(4))(2)].0.5H(2)O,a mixed-valence vanadium(IV,V) phosphate with a pillared layer structure

A mixed-valence vanadium phosphate, NH(4)[(V(2)O(3))(2)(4,4'-bpy)(2)(H(2)PO(4))(PO(4))(2)].0.5H(2)O, has been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. It crystallizes in the monoclinic space group C2/c (No. 15) with a = 12.6354(8) A, b = 9.9786(6) A, c = 23.369(1) A, beta = 92.713(1) degrees, and Z = 4 with R(1) = 0.0389. The structure consists of dimers of edge-sharing vanadium(IV,V) octahedra that are connected by corner-sharing phosphate tetrahedra to form layers in the ab-plane, which are further linked through 4,4'-bipyridine pillars to generate a 3-D framework. Magnetic susceptibility confirms the valence of the vanadium atoms. The (31)P MAS NMR spectrum shows a resonance centered at 80 ppm with a shoulder at ca. 83 ppm in an intensity ratio close to 1:2, which correspond to two distinct P sites. The observed large downfield (31)P NMR shifts can be ascribed to magnetic exchange coupling involving phosphorus atoms. The unpaired electron spin density at the phosphorus nucleus was determined from variable-temperature (31)P NMR spectra. The (1)H MAS NMR spectrum was fitted to six components in accordance with the structure as determined from X-ray diffraction.     

Amine-templated linear vanadium sulfates with different chain structures

Amine-templated vanadium sulfates of the formula [HN(CH(2))(6)NH][(V(IV)O)(2)(OH)(2)(SO(4))(2)].H(2)O, I, [H(3)N(CH(2))(2)NH(3)][V(III)(OH)(SO(4))(2)].H(2)O, II, and [H(2)N(CH(2))(4)NH(2)][(V(IV)O)(H(2)O)(SO(4))(2)], III, have been prepared under hydrothermal conditions. These vanadium sulfates add to the new emerging family of organically templated metal sulfates. Compound I has a linear chain structure consisting of V(2)O(8) square-pyramid dimers connected by corner-sharing SO(4) tetrahedra, creating four-membered rings along the chain. Both II and III possess simple linear chain topologies formed by VO(6) octahedra and SO(4) tetrahedra, with II having the tancoite chain structure. Compound I crystallizes in the triclinic space group P1 (No. 2) with a = 7.4852(4) A, b = 9.5373(5) A, c = 11.9177(6) A, alpha = 77.22 degrees, beta = 76.47(2) degrees, gamma = 80.86 degrees, Z = 2. Compound II: monoclinic, space group P2(1)/c (No. 14), a = 6.942(2) A, b = 10.317(3) A, c = 15.102(6) A, beta = 90.64(4) degrees, Z = 4. Compound III: triclinic, space group P1 (No. 2) with a = 6.2558(10) A, b = 7.0663(14) A, c = 15.592(4) A, alpha = 90.46(2) degrees, beta = 90.47(2) degrees, gamma = 115.68(2) degrees, Z = 2. Magnetic susceptibility measurements reveal weak antiferromagnetic interactions in I and III and ferromagnetic interactions in II.     

Ionic liquid of choline chloride/malonic acid as a solvent in the synthesis of open-framework iron oxalatophosphates

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.     

Synthesis, Structure, and Photoluminescence Property of a Novel One-dimensional Inorganic-organic Hybrid Gallophosphate JGP-2

A novel one-dimensional inorganic-organic hybrid gallophosphate compound, Ga(2,2′-bipy)(HPO4)· (H2PO4)(denoted JGP-2) was synthesized hydrothermally with 2,2′-bipyridine as a ligand and characterized by X-ray powder diffraction (XRD), elemental analysis, inductively coupled plasma(ICP), TGA analysis, solid-state 31P NMR, and luminescence spectra and structurally determined by single-crystal X-ray diffraction analysis. JGP-2 crystallized in the triclinic system, space group Pī(No.2), with a=0.7818(1) nm, b=0...     

New titanium and nickel gallophosphates with layered structures

Two new transition-metal gallophosphates, (H(2)C(4)H(10)N(2))(3)[(Ti(2.5)(H(2)O)(4)Ga(5.5)(PO(4))(10)].2H(2)O (TGP-1) and [H(3.5)(C(4)H(13)N(3))(2)][(Ni(0.5)(OH)(4)Ga(5.5)(PO(4))(3)(HPO(4))(4)].2H(2)O (NGP-1), have been synthesized under mild hydrothermal conditions and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, electron paramagnetic resonance, electron probe microanalysis, and magnetic susceptibility data. TGP-1 exhibits a unique two-dimensional structure consisting of tetrahedral and octahedral metals centers and is the foremost paramagnetic TiGaPO material ever prepared. NGP-1 as well represents the first NiGaPO compound and adopts a layer structure that is constructed from hexameric M-O clusters of trigonal bipyramids and octahedra. In both compounds, the transition metals incorporate with gallium into octahedral sites only, while the four- and five-coordinated metals centers are only Ga(3+) ions. The unique sites for Ti(3+) and Ni(2+) ions have been initially elucidated from single-crystal structure refinements and further confirmed by bond-valence-sum calculations, EPR, and magnetic susceptibility studies. Crystal data: TGP-1, monoclinic, P2(1)/c; a = 25.692(2) A, b = 9.6552(8) A, c = 9.8418(8) A, beta = 96.737(2)(o) , V = 2424.5(3) A(3), and Z = 2; NGP-1, monoclinic, C2/c, a = 20.8363(12) A, b = 11.9546(7) A, c = 16.4577(9) A, beta = 117.285(1)(o) , V = 3643.3(1) A(3), Z = 4.     

Syntheses and crystal structures of a series of alkaline earth vanadium selenites and tellurites

Six new novel alkaline-earth metal vanadium(V) or vanadium(IV) selenites and tellurites, namely, Sr(2)(VO)(3)(SeO(3))(5), Sr(V(2)O(5))(TeO(3)), Sr(2)(V(2)O(5))(2)(TeO(3))(2)(H(2)O), Ba(3)(VO(2))(2)(SeO(3))(4), Ba(2)(VO(3))Te(4)O(9)(OH), and Ba(2)V(2)O(5)(Te(2)O(6)), have been prepared and structurally characterized by single crystal X-ray diffraction analyses. These compounds exhibit six different anionic structures ranging from zero-dimensional (0D) cluster to three-dimensional (3D) network. Sr(2)(VO)(3)(SeO(3))(5) features a 3D anionic framework composed of VO(6) octahedra that are bridged by SeO(3) polyhedra. The oxidation state of the vanadium cation is +4 because of the partial reduction of V(2)O(5) by SeO(2) at high temperature. Ba(3)(VO(2))(2)(SeO(3))(4) features a 0D [(VO(2))(SeO(3))(2)](3-) anion. Sr(V(2)O(5))(TeO(3)) displays a unique 1D vanadium(V) tellurite chain composed of V(2)O(8) and V(2)O(7) units connected by tellurite groups, forming 4- and 10-MRs, whereas Sr(2)(V(2)O(5))(2)(TeO(3))(2)(H(2)O) exhibits a 2D layer consisting of [V(4)O(14)] tetramers interconnected by bridging TeO(3)(2-) anions with the Sr(2+) and water molecules located at the interlayer space. Ba(2)(VO(3))Te(4)O(9)(OH) exhibits a one-dimensional (1D) vanadium tellurite chain composed of a novel 1D [Te(4)O(9)(OH)](3-) chain further decorated by VO(4) tetrahedra. Ba(2)V(2)O(5)(Te(2)O(6)) also features a 1D vanadium(V) tellurites chain in which neighboring VO(4) tetrahedra are bridged by [Te(2)O(6)](4-) dimers. The existence of V(4+) ions in Sr(2)(VO)(3)(SeO(3))(5) is also confirmed by magnetic measurements. The results of optical diffuse-reflectance spectrum measurements and electronic structure calculations based on density functional theory (DFT) methods indicate that all six compounds are wide-band gap semiconductors.     

Hydro/solvothermal synthesis and structures of new zinc phosphates of varying dimensionality

Hydro/solvothermal reactions of ZnO, HCl, H(3)PO(4), 1,4-diazacycleheptane (homopiperazine), and H(2)O under a variety of conditions yielded three new organic-inorganic hybrid materials, [C(5)N(2)H(14)][Zn(HPO(4))(2)].xH(2)O (x = approximately 0.46), I, [C(5)N(2)H(14)][Zn(3)(H(2)O)(PO(4))(2)(HPO(4))], II, and [C(5)N(2)H(14)][Zn(2)(HPO(4))(3)].H(2)O, III. While I has a one-dimensional structure, II possesses a two-dimensional layered structure, and III has a three-dimensional structure closely related to the ABW zeolitic architecture. All the compounds consist of vertex linking of ZnO(4), PO(4), and HPO(4) tetrahedral units. The fundamental building unit, single four-membered ring (S4R), is present in all the cases, and the observed differences in their structures result from variations in the connectivity between the S4R units. Thus I has a corner-shared S4R forming an infinite one-dimensional chain, II has two corner-shared chains fused through a 3-coordinated oxygen atom forming a strip and a layer with eight-membered apertures, and III has S4R units connected via oxygen atoms to give rise to channels bound by eight T atoms (T = Zn, P) in all crystallographic directions. Crystal data: I, monoclinic, space group = P2(1)/n (No. 14), a = 8.6053(3) A, b = 13.7129(5) A, c = 10.8184(4) A, beta = 97.946(1) degrees, V = 1264.35(8) A(3), Z = 4; II, monoclinic, space group = P2(1)/c (No. 14), a = 11.1029(1) A, b = 17.5531(4) A, c = 8.2651(2) A, beta = 97.922(2) degrees, V = 1595.42(5) A(3), Z = 4; III, monoclinic, space group = P2(1) (No. 4), a = 8.0310(2) A, b = 10.2475(3) A, c = 10.570(3) A, beta = 109.651(1) degrees, V = 819.24(3) A(3), Z = 2.     

Hydrothermal Synthesis and Crystal Structure of Iron Molybdophosphate Fe[Mo_6O_(12)(OH)_3(H_2PO_4)(HPO_4)_2(PO_4)]_2- [Fe(2,2′-bipy)(H_2O)_2]_2[Fe(2,2′-bipy)_3]_2·6H_2O

1 INTRODUCTION Organic-inorganic hybrid materials and polyoxo-metalates have received much attention because of their intriguing structural diversity and potential applications in molecular adsorption, ion exchange, heterogeneous catalysis and nanotech nology as well as in electrical, magnetic and photochemical areas[1, 2]. One of the important ad- vances in the design of new organic-inorganic hybrid materials is utilizing poly- oxometalates’ coordination ability to produce poly- oxoanio…     

Non-Template-Centered, Closed Tetravanadium Phosphate and Phosphonate Clusters

Tetranuclear V(III) complexes, [HB(pz)(3)](4)V(4)(&mgr;-C(6)H(5)OPO(3))(4) (I), its acetonitrile solvate (I.4CH(3)CN), and [HB(pz)(3)](4)V(4)(&mgr;-O(2)NC(6)H(4)OPO(3))(4).4C(7)H(8).H(2)O (II), and tetranuclear vanadyl complexes, (t-Bupz)(4)V(4)O(4)(&mgr;-C(6)H(5)PO(3))(4).2H(2)O (III) and (t-Bupz)(5)V(4)O(4)(&mgr;-C(6)H(5)PO(3))(4).4CH(3)CN.0.6 H(2)O (IV), have been prepared and characterized by spectroscopic, magnetic, and electrochemical methods (pz = pyrazole, t-Bupz = tert-butylpyrazole). The use of organic solvents and bulky organic groups as ancillary ligands leads to formation of neutral species instead of the anionic clusters commonly found in the hydrothermal synthesis of vanadium organophosphate/phosphonate systems. Complexes I.4CH(3)CN and IV have also been characterized by single-crystal X-ray diffraction. Crystal data: I.4CH(3)CN, triclinic, P&onemacr;, a = 15.495(3) ?, b = 17.000(3) ?, c = 17.949(4) ?, alpha = 89.17(3) degrees, beta = 86.00(3) degrees, gamma = 78.60(3) degrees, Z = 2; IV, triclinic, P&onemacr;, a = 15.541(3) ?, b = 16.340(2) ?, c = 19.069(5) ?, alpha = 83.58(2) degrees, beta = 79.67(2) degrees, gamma = 63.68(1) degrees, Z = 2. Both are closed clusters, the core structure of the first consisting of a cubane-like arrangement of metal octahedra and phosphate tetrahedra and the core structure of the second consisting of a distorted, collapsed variant of the first. Unlike other vanadium phosphate clusters, these compounds form in the absence of a central, templating agent. As such they represent the simplest form of a closed cluster in which steric forces and cluster connectivity requirements play the primary role in organizing the cluster framework.     

Syntheses, structures, and ion-exchange properties of the three-dimensional framework uranyl gallium phosphates, Cs4[(UO2)2(GaOH)2(PO4)4].H2O and Cs[UO2Ga(PO4)2

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).     

Syntheses and structures of two low-dimensional beryllium phosphate compounds: [C5H14N2]2[Be3(HPO4)5].H2O and [C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5H2O

The first two low-dimensional beryllium phosphates, [C5H14N2]2[Be3(HPO4)5].H2O (BePO-CJ29) and [C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5 H2O (BePO-CJ30), have been successfully synthesized under mild hydrothermal/solvothermal conditions. BePO-CJ29 is built up from strict alternation of BeO4 and HPO4 tetrahedra forming a unique one-dimensional double chains with 12-ring apertures. There are pseudo-10-ring apertures enclosed by two double chains through H-bonds. BePO-CJ29 can also be viewed as a pseudo 2-D layered structure stabilized by strong H-bonds. The diprotonated 2-methylpiperazium cations are located at three positions (i.e., inside the 12-ring aperture, inside the pseudo-10-ring aperture, and in the interlayer of the inorganic pseudo-layers. BePO-CJ30 is constructed by the alternation of Be-centered tetrahedra (including BeO4 and HBeO4) and P-centered tetrahedra (including PO4 and HPO4) resulting in a two-dimensional layered structure parallel to the (0 1 1) direction. The complex layer is composed of coupled 4.8 net sheets. The diprotonated 1,6-hexandiamine cations and water molecules reside in the interlayer regions and interact with the inorganic layers through H-bonds. Crystal data are as follows: [C5H14N2]2[Be3(HPO4)5].H2O (BePO-CJ29), triclinic, P1 (No. 2), a = 8.1000(9) A, b = 8.4841(14) A, c = 19.665(2) A, alpha = 89.683(10) degrees, beta = 78.182(8) degrees, gamma = 87.932(9) degrees, V = 1321.9(3) A3, Z = 2, R1 = 0.0523 (I > 2sigma(I)), and wR2 = 0.1643 (all data); [C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5 H2O (BePO-CJ30), orthorhombic, Pccn (No. 56), a = 26.01(4) A, b = 8.431(12) A, c = 9.598(13) A, V = 2105(5) A3, Z = 8, R1 = 0.0833 (I > 2sigma(I)), and wR2 = 0.2278 (all data).