GeO2 natrolite-type infinite four and eight R-containing layers in a 2D pure-Ge framework: Ge3O5(OH)4[C2N2H10

A new two-dimensional framework germanate, Ge3O5(OH)4[C2N2H10] (denoted ICMM-8), with a 3:9 Ge:O ratio has been synthesized, using a mixture of pyridine, water, and ethanol as the solvent and 1,4-diazabicyclo[2.2.2]octane and ethylenediamine as the structure-directing agents, under solvothermal conditions. The structure was determined by single-crystal X-ray diffraction. In this new compound, the GeO2 natrolite-type infinite four and eight R-containing layers appears for the first time in a pure GeO2 framework. The total 2D structure is built up from SBU-6, four tetrahedra, and two octahedra. The hydroxyl groups occupy four positions of each octahedral germanium atom. The compound is characterized by IR spectra and TGA-DTA. Crystal data: Ge3O5(OH)4[C2N2H10], monoclinic space group P2(1)/c; a = 11.3570(9) Angstroms, b = 8.8819(7) Angstroms, c = 9.9200(8) Angstroms, beta = 90.710(1), V = 1000.6(1) Angstroms(3), Z = 4, R(1) = 0.044 (I > 2(I)), and wR(2) = 0.1051 (all data).     

(C4N3H15)[(BO2)2(GeO2)4]: the first organically templated 3D borogermanate showing 1D 12-rings, large channels, and a novel zeolite-type framework topology constructed from Ge8O24 and B2O7 cluster units

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.     

Hydrothermal synthesis and structural characterization of a new organically templated germanate,Ge(10)O(21)(OH).N(4)C(6)H(21)

A new open-framework germanium oxide Ge(10)O(21)(OH).N(4)C(6)H(21) has been hydrothermally synthesized at 180 degrees C for 6 days by using the tris(2-aminoethyl)amine (tren) molecule as a structure-directing agent. This compound was characterized by means of single-crystal X-ray diffraction and FTIR. It crystallizes in the noncentric monoclinic system Cm (a = 14.0495(2) A, b = 12.8058(3) A, c = 9.2637(2) A, beta = 128.406(1) degrees, Z = 4). Its three-dimensional framework is built up from GeO(4) and GeO(3)(OH) tetrahedra connected by vertexes to GeO(5) trigonal bipyramids and GeO(6) octahedra. A pseudo-cubic building unit ("4-3" subunit) consists of four GeO(4) tetrahedra, two GeO(5) trigonal bipyramids, and one GeO(6) octahedron (Ge(7)). In the "4-3" block, the GeO(5) trigonal bipyramids share a common edge. This Ge(7) entity is linked to three tetrahedral units GeO(3)X (X = O, OH), and this forms an original decameric building unit Ge(10)O(21)(OH) which is new in the germanates crystal chemistry. It results in a relatively dense open framework composed of pear-shape cavities (7(8)6(2)5(2)4(4)3(2)) encapsulating the triprotonated tren molecule. The inorganic network contains small pores delimited by 7-ring channels running along [001].     

K2[Ge(B4O9)].2H2O: a unique 3D alternating linkage mode of a B4O9 cluster and GeO4 unit in borogermanate with two pairs of interweaving double helical channels

The first noncentrosymmetric potassium templated borogermanate, K(2)[Ge(B(4)O(9))].2H(2)O, has been solvothermally synthesized and characterized by IR, SEM, powder X-ray diffraction (PXRD), TGA, energy dispersive spectroscopy (EDS), single crystal X-ray diffraction, and second harmonic generation (SHG) activity, respectively. This compound crystallized in the monoclinic space group Cc with a = 6.793(1) A, b = 12.0699(3) A, c = 11.895(3) A, beta = 91.156(4) degrees, V = 975.1(4) A(3), and Z = 4. Interestingly, the structure possesses a unique 3D alternating linkage mode of B(4)O(9) clusters and GeO(4) units and contains two pairs of interweaving double helical channels with a 10-membered ring. In one, the right- and left-handed helices couple each other, and in the other, the left- and right-handed helices couple together. The compound exhibits distinct nonlinear optical (NLO) properties because it lacks a symmetric center. Furthermore, the framework of the title compound not only displays high thermal stability but also can be recoverable to a large degree during a dehydration-hydration cycle.     

Hydrothermal single-crystal growth in the systems Ag/Hg/X/O (X = VV, AsV): crystal structures of (Ag3Hg)VO4, (Ag2Hg2)3(VO4)4, and (Ag2Hg2)2(HgO2)(AsO4)2 with the unusual tetrahedral cluster cations (Ag3Hg)3+ and (Ag2Hg2)4+ and crystal structure of AgHgVO4

Single crystals of (Ag3Hg)VO4 (I), (Ag2Hg2)3(VO4)4 (II), AgHgVO4 (III), and (Ag2Hg2)2(HgO2)(AsO4)2 (IV) were grown under hydrothermal conditions (250 degrees C, 5 d) from starting mixtures of elementary mercury, silver nitrate, ammonium vanadate, and disodium hydrogenarsenate, respectively. All crystal structures were determined from X-ray diffraction data, and their chemical compositions were confirmed by electron microprobe analysis. I crystallizes in the tillmannsite structure, whereas II-IV adopt new structure types: (I) I4, Z = 2, a = 7.7095(2) A, c = 4.6714(2) A, 730 structure factors, 24 parameters, R[F2 > 2sigma(F2)] = 0.0365; (II) I42d, Z = 4, a = 12.6295(13) A, c = 12.566(3) A, 1524 structure factors, 55 parameters, R[F2 > 2sigma(F2)] = 0.0508; (III) C2, Z = 4, a = 9.9407(18) A, b = 5.5730(8) A, c = 7.1210(19) A, beta = 94.561(10) degrees , 1129 structure factors, 48 parameters, R[F2 > 2sigma(F2)] = 0.0358; (IV) P31c, Z = 2, a = 6.0261(9) A, c = 21.577(4) A, 1362 structure factors, 52 parameters, R[F2 > 2sigma(F2)] = 0.0477. The most striking structural features of I, II, and IV are the formation of tetrahedral cluster cations (Ag3Hg)3+ and (Ag2Hg2)4+, respectively, built of statistically distributed Ag and Hg atoms with a metal-metal distance of about 2.72 A. The electronic structure of these clusters can formally be considered as two-electron-four-center bonding. The crystal structure of III differs from the protrusive structure types insofar as silver and mercury are located on distinct crystallographic sites without a notable metal-metal interaction >3.55 A. All crystal structures are completed by tetrahedral oxo anions XO4(3-) (X = VV, AsV) and for IV additionally by a mercurate group, HgO2(2-).     

Crystal Structure of 3-Methyl-4-methoxy-3-(3-methyl-4- methoxy-2-benzofuranyl) -2-H-benzofuranyl

1　ＩＮＴＲＯＤＵＣＴＩＯＮ3ｍｅｔｈｙｌ4ｈｙｄｒｏｘｙｂｅｎｚｏｆｕｒａｎｉｓａｎｉｎｔｅｒｍｅｄｉａｔｅｕｓｅｄｆｏｒｔｈｅｓｙｎｔｈｅｓｉｓｏｆｎａｔｕｒｅｐｒｏｄｕｃｔｓ[1].Ｉｔｈａｓｂｅｅｎｓｙｎｔｈｅｓｉｚｅｄｆｒｏｍ1,3ｄｉｈｙｄｒｏｘｙｂｅｎｚｅｎｅ[2-3].Ｔｏｓｙｎｔｈｅｓｉｚｅａｂｉｅｔａｎｅｑｕｉｎｏｎｅｄｉｔｅｒｐｅｎｏｉｄｓｗｉｔｈｉｔ[4,5],ｗｅｉｎｔｅｎｄｅｄｔｏｐｒｏｔｅｃｔｔｈｅｈｙｄｒｏｘｙａｔｔａｃｈｅｄｔｏｉｔｗｉｔｈＭｅ2ＳＯ4.Ｆｉｎａｌｌｙ,ｔｗｏｃｏｍｐｏｕ…     

Synthesis and Structure of [Er4（μ3—OH）4（Hpro）4（Pro）2（H2O）7]（ClO4）6.7H2O

1 INTRODUCTION The design and synthesis of polynuclear com- plexes have attracted chemists?attention in the contemporary chemistry, since their clusters maybe lead to novel materials with magnetic, optical, electronic and catalytic properties of the constituent metals[1～3]. It is also prevalently interesting to synthesize high-nuclearity metal complexes for their nanoscopic dimensions[3, 4]. Spectroscopic properties of the lanthanides are widely used in the study of biological systems. …     

Synthesis and Crystal Structure of 5,5-Dimethyl-2-(4-chlorophenyl)(3-hydroxy-5,5-dimethyl-2-cyclohexen-1-one-2-yl)methyl-3-(4-methoxyphenylamino)-2-cyclohexene-1-one

The title compound 5,5-dimethyl-2-(4-chlorophenyl)(3-hydroxy-5,5-dimethyl-2-cyclohexen-1-one-2-yl)methyl-3-(4-methoxyphenylamino)-2-cyclohexen-1-one has been synthesized,and its crystal structure was characterized by X-ray single-crystal diffraction. The crystal belongs to monoclinic,space group P21/c with a=9.4193(13),b=26.915(4),c=21.188(3),β =101.906(3)°,V =5256.2(13)3,Z =4,C60H68Cl2N2O8,Mr=1016.06,Dc=1.284 g/cm3,F(000)=2160,λ(MoKα)=0.71073,μ=0.182 mm–1,R=0.0530 and wR=0.1131 for 4128 observed reflections (I>2σ(I)). X-ray analysis reveals that there are two independent molecules in the unit and the cyclohexenone rings adopt different conformations. In addition,there are four intramolecular hydrogen bonds in the title molecule.     

Organically templated uranium(IV) fluorooxalates with layer structures: (H4TREN)[U2F6(C2O4)3].4H2O (TREN = tris(2-aminoethyl)amine) and (H4APPIP)[U2F6(C2O4)3].4H2O (APPIP = 1,4-bis(3-amino-propyl)piperazine)

Two organically-templated layered uranium(IV) fluorooxalates, (H(4)TREN)[U(2)F(6)(C(2)O(4))(3)].4H(2)O (1) (TREN = tris(2-aminoethyl)amine) and (H(4)APPIP)[U(2)F(6)(C(2)O(4))(3)].4H(2)O (2) (APPIP = 1,4-bis(3-aminopropyl)piperazine), have been synthesized by hydrothermal methods and structurally characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic susceptibility. Both structures consist of anionic [U(2)F(6)(C(2)O(4))(3)](4-) layers separated by organic ammonium cations and lattice water molecules. The UF(3)O(6) polyhedra are connected by oxalate ligands in different ways within the layers. They are the first examples of organically-templated uranium fluorooxalates. Crystal data for compound 1 follow: monoclinic, P2(1)/c (No. 14), a = 19.1563(5) A, b = 8.9531(2) A, c = 16.6221(4) A, beta = 114.633(1) degrees, and Z = 4. Crystal data for compound are the same as those for 1 except a = 10.3309(8) A, b = 15.564(1) A, c = 17.537(1) A, and beta = 95.430(4) degrees.     

Synthesis and characterization of [PtIn6](GeO4)2O and its solid solution [PtIn6](GaO4)(2-x)(GeO4)xOx/2 (0 < or = x < or = 2): gradual color change of the solid solution from black (x = 0) to yellow (x = 2) as a consequence of quantum dot effect

A new phase [PtIn6](GeO4)2O, a filled variant of [PtIn6](GaO4)2, and the solid solution [PtIn6](GaO4)(2-x)(GeO4)xOx/2 (0 < or = x < or = 2) were prepared and characterized. Single-crystal structure refinements show that [PtIn6](GeO4)2O is isotypic with the mineral, sulfohalite Na6FCl(SO4)2, and crystallizes in the space group Fmm (Z = 4) with a = 1006.0(1) pm. The building units of [PtIn6](GeO4)2O are isolated [PtIn6]10+ octahedra and (GeO4)4- tetrahedra, and the isolated O2- ions occupy the centers of the In6 octahedra made up of six adjacent PtIn6 octahedra. The lattice parameter of the solid solution [PtIn6](GaO4)(2-x)(GeO4)xOx/2 (0 < or = x < or = 2) varies gradually from a = 1001.3(1) pm at x = 0 to a = 1006.0(1) pm at x = 2, and the color of the solid solution changes gradually from black (x = 0) to red (x = 1) to yellow (x = 2). The cause for the gradual color change was examined by performing density functional theory electronic structure calculations for the end members [PtIn6](GaO4)2 and [PtIn6](GeO4)2O. Our analysis indicates that an oxygen atom at the center of a In6 octahedron cuts the In 5p/In 5p bonding interactions between adjacent [PtIn6]10+ octahedra thereby raising the bottom of the conduction bands, and the resulting quantum dot effect is responsible for the color change.     

Hydrothermal Synthesis and Structure of a New Two- dimensional Zincophosphite:Zn2(HPO3)3(H2DACH (DACH = 1,2-diaminocyclohexane)

A new open-framework zincophosphite, Zn2(HPO3)3(H2DACH 1, was hydrothermally synthesized in the presence of 1,2-diaminocyclohexane (DACH) as structure-directing agent. Its structure was determined by single-crystal X-ray diffraction and further characterized by FTIR, elemental analysis, powder X-ray diffraction and thermogravimetric analysis. Crystal data for 1: Mr = 486.88, monoclinic, space group P21/c with a = 10.2287(11), b = 9.7624(11), c = 16.1686(18) A,β = 92.573(2), V = 1612.9(3) A3, Z = 4, Dc = 2.005 g/cm3, F(000) = 984, μ = 3.314 mm-1 and S = 1.152. The final R = 0.0473 and wR = 0.1121 for 2456 observed reflections with I > 2σ(I). The inorganic layer consisting of four- and eight-membered rings is constructed of alternating ZnO4 tetrahedra and HPO3 pseudo pyramids by sharing vertices. The organic template molecules reside in the interlayer region and interact with the inorganic network through H-bonds.     

Synthesis and Crystal Structure of Ethyl 4-（2-Chloro-4-fluorophenyl）-6-hydroxy-3-oxo-1,3-dihydro-5-isobenzofurancarboxylate

The crystal structure of the title compound(C17H12ClFO5,Mr=350.72) was determined by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21/c,with a=7.693(1),b=15.767(1),c=12.986(1),β=97.23(1)°,V=1562.6(2)3,Z=4,Dc= 1.491 g/cm3,λ(MoKα)=0.71073,F(000)=720,μ(MoKα)=0.280 mm-1,R=0.0563 and wR=0.1674.A total of 3592 unique reflections were collected,of which 2462 with Ⅰ2σ(Ⅰ) were observed.Five-membered lactone rings and hydroxyl-substituted phenyl rings are approximately coplanar with their dihedral angle of 4.1°.The dihedral angle between two different phenyl rings is 71.3°.To our interest,intramolecular O(1)-H(1)···O(4) hydrogen bonds could be found in each molecule.Intramolecular hydrogen bonds and intermolecular van der Waals force contribute to the stability of the structure.     

具有螺旋结构的新型硼磷酸盐化合物:(NH4)0.5(H3O)0.5Mg(H2O)2BP2O8

利用水热方法合成新型硼磷化合物:(NH4)0.5(H3O)0.5Mg(H2O)2BP2O8,单晶X射 线衍射分析证明化合物属六方晶系,空间群为P6522,a=0.94507(19)nm,c=1.5803(5) nm,γ=120°,V=1.2224(5)nm^3,Mr=279.06,Dc=2.258g/cm^3,Z=6,F(000)=834,μ =0.663mm^-1。结构中BO4,PO4基团形成∞^1{[BP2O8]^3-}的螺旋带与MgO6相连构 成八面体-四面体空间骨架,元素分析、IR光谱、热重差热分析和电荷平衡计算证 明晶体中含有NH4^+和质子。NH4^+占据螺旋带螺旋纹内,质子化的水分靠近螺旋带 通道的内侧,两者均起到平衡电荷和稳定骨架的作用。     

U(VI) uranyl cation-cation interactions in framework germanates

The isomorphous compounds NH(4)[(UO(6))(2)(UO(2))(9)(GeO(4))(GeO(3)(OH))] (1), K[(UO(6))(2)(UO(2))(9)(GeO(4))(GeO(3)(OH))] (2), Li(3)O[(UO(6))(2)(UO(2))(9)(GeO(4))(GeO(3)(OH))] (3), and Ba[(UO(6))(2)(UO(2))(9)(GeO(4))(2)] (4) were synthesized by hydrothermal reaction at 220 °C. The structures were determined using single crystal X-ray diffraction and refined to R(1) = 0.0349 (1), 0.0232 (2), 0.0236 (3), 0.0267 (4). Each are trigonal, P(3)1c. 1: a = 10.2525(5), c = 17.3972(13), V = 1583.69(16) ?(3), Z = 2; 2: a = 10.226(4), c = 17.150(9), V = 1553.1(12) ?(3), Z = 2; 3: a = 10.2668(5), c = 17.0558(11), V = 1556.94(15) ?(3), Z = 2; 4: a = 10.2012(5), c = 17.1570(12), V = 1546.23(15) ?(3), Z = 2. There are three symmetrically independent U sites in each structure, two of which correspond to typical (UO(2))(2+) uranyl ions and the other of which is octahedrally coordinated by six O atoms. One of the uranyl ions donates a cation-cation interaction, and accepts a different cation-cation interaction. The linkages between the U-centered polyhedra result in a relatively dense three-dimensional framework. Ge and low-valence sites are located within cavities in the framework of U-polyhedra. Chemical, thermal, and spectroscopic characterizations are provided.     

三维无机-有机杂化微孔化合物Mn3(BTC)2(DMF)4的合成与结构

传统的沸石和分子筛微孔晶体材料是指以硅酸盐、硅铝酸盐、磷铝酸盐和无机金属磷酸盐为骨架的晶体材料．近年来,利用刚性和热稳定性较好的有机分子(如芳香多酸和多碱)和金属离子作为结构单元制备出了新型的无机一有机杂化微孔晶体材料．这类晶体材料能够在去除孔道中的溶剂分     

Synthesis and Crystal Structure of（E）-Ethyl 2-（5-（3-methyl-2-butenyloxy）-2-（3-（4-（3-methyl-2-butenyloxy）phenyl）acryloyl）phenoxy）acetate

The title compound,(E)-ethyl 2-(5-(3-methyl-2-butenyloxy)-2-(3-(4-(3-methyl-2-butenyloxy)phenyl) acryloyl) phenoxy)acetate(1),has been synthesized and characterized by FT-IR and 1H-NMR spectroscopy,ESI-MS,and X-ray single-crystal diffraction.FT-IR,1H-NMR and ESI-MS confirm the functional groups,particularly the ethyl groups in the ester moiety,of the compound.The single-crystal X-ray diffraction has revealed a monoclinic structure,space group P21/n with a = 14.6832(14),b = 7.7581(7),c = 23.075(2),β = 101.670(2)o,V = 2574.2(4) ?3,Z = 4,Dc = 1.235 g/cm,μ = 0.085 mm-1,and F(000) = 1024.The skeleton of chalcone in the molecular structure is coplanar.     

New Synthesis and Molecular Structure of 2-(4'-Methoxyphenyl)-2,4-dithia-1,3,2-diazaphospholidine-5,1'-spirocyclohexane

1 INTRODUCTION Our continuous efforts to look for biologically active heterocyclic compounds led to a new and efficient synthesis of phosphoroheterocycles 1, 3, 2-diazaphospholidine-4-thione 2-sulfides in good yields by the treatment of Lawesson磗 reagent with various -aminonitriles in one-pot procedure. Many approaches to synthesize such phosphoroheterocycles have been reported[1~4]. The common pathways leading to 1, 3, 2-diazaphospho- lidine-4-thione(one) 2-sulfide(oxide) are using t…     

Crystal and Molecular Structure of 5，6，7，8，9，10－Hexahydro－3－（4－methylphenylamino）－2－thioxoquinoxaline

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Direct formation of Ge-C bonds from GeO(2)

Germanium dioxide in the presence of 5% KOH reacted with dimethyl carbonate (DMC) at 250 degrees C to give (MeO)(4)Ge. The reaction of GeO(2) and DMC is similar to that reported for SiO(2); however, the rate of reaction for germanium is much higher than that of the corresponding silicon reaction. In a side-by-side experiment using SiO(2) and GeO(2) where the surface area of the silicon dioxide was 2 orders of magnitude higher than that of the GeO(2), the base-catalyzed reaction with DMC was about an order of magnitude higher for the germanium dioxide. When GeO(2) and 5% KOH were reacted with DMC at 350 degrees C, two products formed: (MeO)(4)Ge (70%) and MeGe(OMe)(3) (30%). Confirmation of the identity of MeGe(OMe)(3) was by GCMS, (1)H and (13)C NMR, and comparison to an authentic sample made by reaction of MeGeCl(3) with NaOMe. Experiments to determine the mechanism of the direct formation of Ge-C from GeO(2) ruled out participation from CO, H(2), or carbon. The KOH-catalyzed reaction of other metal oxides was explored including B(2)O(3), Ga(2)O(3), TiO(2), Sb(2)O(3), SnO(2), and SnO. Boron reacted to give unknown volatile products. Antimony reacted to give a solid which analyzed as Sb(OMe)(3). SnO reacted with DMC to give a mixture that included (MeO)(4)Sn and possibly Me(3)Sn(OMe).     

Hydrothermal Synthesis and Structure of a New Two-dimensional Zincophosphite: Zn_2(HPO_3)_3·H_2DACH(DACH = 1,2-diaminocyclohexane)

1 INTRODUCTION Organically templated metal phosphates have attracted considerable attention in recent years be- cause of their potential applications in catalysis, ion exchange and separation[1]. Among these, zinc phos- phates constitute an important fam…