Synthesis and Structure of Two New Strontium Germanium Nitrides: Sr(3)Ge(2)N(2) and Sr(2)GeN(2)

We report the structures of two new strontium germanium nitrides synthesized as crystals from the elements in sealed Nb tubes at 750 degrees C using liquid Na as a growth medium. Sr(3)Ge(2)N(2) is isostructural with the previously reported Ba analogue. It crystallizes in P2(1)/m (No. 11), with a = 9.032(2) ?, b = 3.883(1) ?, c = 9.648(2) ? and beta = 112.42(3) degrees, and has two formula units per unit cell. It contains GeN(2)(4)(-) units and additionally |Ge(2)(-) zigzag chains. Sr(2)GeN(2) crystallizes in P4(2)/mbc (No. 135) with a= b = 11.773(2) ? and c= 5.409(1) ? and has Z = 8. It also contains GeN(2)(4)(-) units which have 18 valence electrons and, consequently are bent, like the isoelectronic molecule SO(2).     

Synthesis and structure of alkaline earth silicon nitrides: BaSiN(2), SrSiN(2), and CaSiN(2)

The alkaline earth silicon nitrides AESiN(2) (AE = Ca, Sr, Ba) are reported, synthesized as clear, colorless, single crystals from molten sodium at 900-1100 degrees C or, in the cases of BaSiN(2) and SrSiN(2), as white powders by reacting powdered intermetallics AESi with flowing anhydrous ammonia at 550-1000 degrees C. Structures were determined from single-crystal X-ray diffraction measurements at 150 K: BaSiN(2) crystallizes in space group Cmca (No. 64) with a = 5.6046(1) A, b = 11.3605(3) A, c = 7.5851(2) A, and Z = 8. The structure consists of pairs of SiN(4) tetrahedra edge-linked to form bow-tie-shaped Si(2)N(6) dimers which share vertexes to form layers and has no analogue in oxide chemistry. SrSiN(2) has a distorted form of this structure (SrSiN(2): space group P2(1)/c (No. 14), a = 5.9750(5) A, b = 7.2826(7) A, c = 5.4969(4) A, beta = 113.496(4) degrees, Z = 4). The structure of CaSiN(2) contains only vertex-sharing SiN(4) tetrahedra, linked to form a three-dimensional stuffed-cristobalite type framework isostructural with KGaO(2) (CaSiN(2): space group Pbca (No. 61), a = 5.1229(3) A, b = 10.2074(6) A, c = 14.8233(9) A, Z = 16).     

Crystal structures of two polymorphs of Ca3[Al2N4

Green transparent single crystals of alpha-Ca3[Al2N4] (monoclinic, P2(1)/c, No. 14, a = 957.2(3) pm, b = 580.2(3) pm, c = 956.3(5) pm, beta = 111.62(3) degrees; Z = 4) were obtained from reactions of mixtures of the representative metals with nitrogen above temperatures of 1000 degrees C. beta-Ca3[Al2N4] (monoclinic, C2/c, No. 15, a = 1060.6(2) pm, b = 826.0(2) pm, c = 551.7(1) pm, beta = 92.1(1) degrees; Z = 4) was formed as a byproduct of a reaction of calcium with alumina under nitrogen at T = 930 degrees C in form of colorless crystals. The crystal structures of the two polymorphs contain edge- and corner-sharing AlN4 tetrahedra, leading to different layered anionic partial structures: infinity 2[AlN2/2N2/3)2(AlNN2/2N1/3)6/3(12-)] in the alpha-phase and infinity 2[Al2N2N4/2(6-)] in the beta-polymorph.     

Diverse polyanions based on MnBi4 and MnSb4 tetrahedra: polymorphism, structure, and bonding in Ca21Mn4Bi18 and Ca21Mn4Sb18

New transition-metal-containing Zintl phases, Ca21Mn4Bi18 and Ca21Mn4Sb18, have been synthesized by high-temperature reactions, and their structures have been determined by single-crystal X-ray diffraction. Ca21Mn4Bi18 crystallizes in the monoclinic space group C2/c (No. 15, Z = 4) with a = 17.470(2) A, b = 17.392(2) A, c = 17.208(2) A, beta = 93.253(2) degrees (R1 = 0.0405, wR2 = 0.0840) and is isostructural with the recently reported Ca21Mn4Sb18. The compound with the same formula, which is also reported herein, is in turn a new polymorph of Ca21Mn4Sb18 and crystallizes in the monoclinic space group C2/m (No. 12, Z = 4) with a = 17.415(6) A, b = 16.567(6) A, c = 17.047(6) A, beta = 92.068(4) degrees (R1 = 0.0432, wR2 = 0.0788). This new polymorph of Ca21Mn4Sb18 is isostructural with another related compound, Sr21Mn4Sb18. Despite the similarity in their chemical formulas, the structures of Ca21Mn4Bi18 and Ca21Mn4Sb18 are very different: Ca21Mn4Bi18 contains unique [Mn4Bi10] cluster anions made up of four MnBi4 tetrahedra connected through edge-sharing. The structure of Ca21Mn4Sb18 features edge- and corner-shared MnSb4 tetrahedra, which make [Mn4Sb11] tetramers. The latter are linked to each other through external Sb-Sb bonds to form larger isolated [Mn8Sb22] polyanions. Electronic band structure calculations performed using the TB-LMTO-ASA method show a small band gap at the Fermi level, suggesting narrow-gap semiconducting behavior for both compounds.     

Sr11Ge4N6: a new nitride composed of [GeN2Sr7]4+ antiperovskite-type slabs and [Sr4Ge]4+ layers, separated by sheets of bent [Ge(II)N2]4- ions

The layered nitride Sr11Ge4N6 contains Ge4- Zintl anions in both [Sr4Ge]4+ layers and [GeN2Sr7]4+ antiperovskite-type slabs which are separated by sheets of bent [Ge(II)N2]4- ions; the observed range of formal germanium oxidation states in nitrides thus extends between +4 and -4.     

Synthesis and characterization of six new quaternary actinide thiophosphate compounds: Cs(8)U(5)(P(3)S(10))(2)(PS(4))(6)(,) K(10)Th(3)(P(2)S(7))(4)(PS(4))(2), and A(5)An(PS(4))(3), (A = K, Rb, Cs; An = U, Th)

Six new actinide metal thiophosphates have been synthesized by the reactive flux method and characterized by single-crystal X-ray diffraction: Cs(8)U(5)(P(3)S(10))(2)(PS(4))(6) (I), K(10)Th(3)(P(2)S(7))(4)(PS(4))(2) (II), K(5)U(PS(4))(3) (III), K(5)Th(PS(4))(3) (IV), Rb(5)Th(PS(4))(3) (V), and Cs(5)Th(PS(4))(3) (VI). Compound I crystallizes in the monoclinic space group P2(1)/c with a = 33.2897(1) A, b = 14.9295(1) A, c = 17.3528(2) A, beta = 115.478(1) degrees, Z = 8. Compound II crystallizes in the monoclinic space group C2/c with a = 32.8085(6) A, b = 9.0482(2) A, c = 27.2972(3) A, beta = 125.720(1) degrees, Z = 8. Compound III crystallizes in the monoclinic space group P2(1)/c with a = 14.6132(1) A, b = 17.0884(2) A, c = 9.7082(2) A, beta = 108.63(1) degrees, Z = 4. Compound IV crystallizes in the monoclinic space group P2(1)/n with a = 9.7436(1) A, b = 11.3894(2) A, c = 20.0163(3) A, beta = 90.041(1) degrees, Z = 4, as a pseudo-merohedrally twinned cell. Compound V crystallizes in the monoclinic space group P2(1)/c with a = 13.197(4) A, b = 9.997(4) A, c = 18.189(7) A, beta = 100.77(1) degrees, Z = 4. Compound VI crystallizes in the monoclinic space group P2(1)/c with a = 13.5624(1) A, b = 10.3007(1) A, c = 18.6738(1) A, beta = 100.670(1) degrees, Z = 4. Optical band-gap measurements by diffuse reflectance show that compounds I and III contain tetravalent uranium as part of an extended electronic system. Thorium-containing compounds are large-gap materials. Raman spectroscopy on single crystals displays the vibrational characteristics expected for [PS(4)](3)(-), [P(2)S(7)](4-), and the new [P(3)S(10)](5)(-) building blocks. This new thiophosphate building block has not been observed except in the structure of the uranium-containing compound Cs(8)U(5)(P(3)S(10))(2)(PS(4))(6).     

(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.     

New framework connectivity patterns in templated networks: the creatinine zinc phosphites C4N3OH7.ZnHPO3, C4N3OH7.Zn(H2O)HPO3, and (C4N3OH7)2.ZnHPO3.H2O

The syntheses, crystal structures, and properties of C(4)N(3)OH(7).ZnHPO(3), C(4)N(3)OH(7).Zn(H(2)O)HPO(3), and (C(4)N(3)OH(7))(2).ZnHPO(3).H(2)O are reported. These new creatinine zinc phosphites are built up from networks of vertex-sharing HPO(3) pseudopyramids and various types of ZnO(2)N(2), ZnO(3)N, and ZnO(2)N(H(2)O) tetrahedra, resulting in extended structures of different dimensionalities (as sheets, clusters, and chains, respectively). They demonstrate the structural effect of incorporating "terminal" (nonnetworking) Zn-N and Zn-OH(2) moieties into zinc centers. Crystal data: C(4)N(3)OH(7).ZnHPO(3), triclinic, P1 (No. 2), a = 8.9351(4) A, b = 9.5011(4) A, c = 9.9806(4) A, alpha = 87.451(1) degrees, beta = 85.686(1) degrees, gamma = 89.551(1) degrees, Z = 4; C(4)N(3)OH(7).Zn(H(2)O)HPO(3), monoclinic, P2(1)/c (No. 14), a = 10.1198(7) A, b = 7.2996(5) A, c = 13.7421(9) A, beta = 107.522(1) degrees, Z = 4; (C(4)N(3)OH(7))(2).ZnHPO(3).H(2)O, triclinic, P1 (No. 2), a = 10.7289(6) A, b = 10.9051(6)A, c = 13.9881(8) A, alpha = 89.508(1) degrees, beta = 74.995(1) degrees, gamma = 74.932(1) degrees, Z = 4.     

Hydrothermal synthesis of organic-inorganic hybrid materials: network structures of the bimetallic oxides [M(Hdpa)2V4O12] (M = Co, Ni, dpa = 4,4'-dipyridylamine)

The hydrothermal reactions of MCl(2).6H2O (M = Co, Ni) NaVO3, 4,4'-dipyridylamine (dpa), and H2O yield materials of the type [M(Hdpa)2V4O12] (M = Co (1), Ni (2)). The two-dimensional structures of 1 and 2 are constructed from bimetallic oxide networks (MV4O12)n2n- with monodentate Hdpa projecting the protonated ring into the interlamellar region. The oxide network may be described as ruffled chains of corner-sharing (VO4) tetrahedra linked by (NiO4N2) octahedra into the two-dimensional assembly. Crystal data: C10H10Co0.5N3O6V2(1), monoclinic P2(1)/c, a = 10.388(1) A, b = 7.6749(7) A, c = 16.702(2) A, beta = 102.516(1) degrees, Z = 4. C10H10N3Ni0.5O6V2 (2), monoclinic, P2(1)/c, c = 10.3815(2) A, b = 7.7044(2) A, c = 16.6638(4) A, beta = 102.573(1) degrees, Z = 4.     

Crystal Structure of 2-Germatranylmethyl-N-(4'-methylphenyl) succinimide

1INrnODUCTIONItiswell-knownthatitaconicacidderivativesandgermatraneshavemanybioac-tivitiest1.23.lnordertoinvestigatethestructureandantitumoractivitiesofnewger-maniumcompounds,wesynthesizedaseriesofpolycycliccompoundsbythereactionoftrichlorogermanewith2-succinimidesor2-methylenesuccinamicacids[3i.Aspartofthiswork,n0wwereP0rtinthispaPerthecrystalstructureofthetitlec0mpound.2EXPERIMENTAL2-Germatranylmethyl-N-(4'-methylphenyl)succinimidewassynthesizedasacolourlesscrystal,anditsstructureh…     

Mixed-metal uranium(VI) iodates: hydrothermal syntheses,structures, and reactivity of Rb[UO(2)(CrO(4))(IO(3))(H(2)O)], A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K,Rb, Cs), and K(2)[UO(2)(MoO(4))(IO(3))(2)

The reactions of the molecular transition metal iodates A[CrO(3)(IO(3))] (A = K, Rb, Cs) with UO(3) under mild hydrothermal conditions provide access to four new, one-dimensional, uranyl chromatoiodates, Rb[UO(2)(CrO(4))(IO(3))(H(2)O)] (1) and A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K (2), Rb (3), Cs (4)). Under basic conditions, MoO(3), UO(3), and KIO(4) can be reacted to form K(2)[UO(2)(MoO(4))(IO(3))(2)] (5), which is isostructural with 2 and 3. The structure of 1 consists of one-dimensional[UO(2)(CrO(4))(IO(3))(H(2)O)](-) ribbons that contain uranyl moieties bound by bridging chromate and iodate anions as well as a terminal water molecule to create [UO(7)] pentagonal bipyramidal environments around the U(VI) centers. These ribbons are separated from one another by Rb(+) cations. When the iodate content is increased in the hydrothermal reactions, the terminal water molecule is replaced by a monodentate iodate anion to yield 2-4. These ribbons can be further modified by replacing tetrahedral chromate anions with MoO(4)(2)(-) anions to yield isostructural, one-dimensional [UO(2)(MoO(4))(IO(3))(2)](2)(-) ribbons. Crystallographic data: 1, triclinic, space group P(-)1, a = 7.3133(5) A, b = 8.0561(6) A, c = 8.4870(6) A, alpha = 88.740(1) degrees, beta = 87.075(1) degrees, gamma = 71.672(1) degrees, Z = 2; 2, monoclinic, space group P2(1)/c, a = 11.1337(5) A, b = 7.2884(4) A, c = 15.5661(7) A, beta = 107.977(1) degrees, Z = 4; 3, monoclinic, space group P2(1)/c, a = 11.3463(6) A, b = 7.3263(4) A, c = 15.9332(8) A, beta = 108.173(1) degrees, Z = 4; 4, monoclinic, space group P2(1)/n, a = 7.3929(5) A, b = 8.1346(6) A, c = 22.126(2) A, beta = 90.647(1) degrees, Z = 4; 5, monoclinic, space group P2(1)/c, a = 11.3717(6) A, b = 7.2903(4) A, c = 15.7122(8) A, beta = 108.167(1) degrees, Z = 4.     

Dinuclear and layered copper 2-pyridylphosphonates with weak ferromagnetism observed in layer compound Cu(C5H4NPO3)

This paper reports the syntheses and structures of three new copper phosphonates based on 2-pyridylphosphonate, namely, Cu(C(5)H(4)NPO(3)H)2 (1), Cu3(OH)2(C(5)H(4)NPO(3))2.2H2O (2) and Cu(C(5)H(4)NPO(3)) (3). Compound 1 has a discrete dimeric structure in which the {CuO(4)N} square pyramids are linked by the {CPO(3)} tetrahedra through corner-sharing. The dimers are further connected into a chain through hydrogen bonds. In compound 2, edge-sharing {Cu(1)O(4)N} square pyramids and {Cu(2)O(4)} planes are found to form an infinite chain with composition {Cu(3)(mu-OH)(2)(mu-O)(4)}. Neighboring chains are linked by the phosphonate groups of the 2-pyridylphosphonate ligands, resulting in inorganic layers containing 4-, 8- and 12-membered rings. The pyridyl groups and the lattice water molecules occupy the inter-layer space. In compound 3, the {Cu(1)O(4)} and {Cu(2)O(2)N(2)} planes are each corner-shared with the {CPO(3)} tetrahedra, forming an inorganic layer containing 8- and 16-membered rings. The pyridyl groups reside between the layers. Crystal data for 1: space group P(-)1, a = 8.4045(19), b = 8.751(2), c = 10.632(2) A, alpha = 66.673(4), beta = 72.566(4), gamma = 70.690(4) degrees , V = 664.7(2) A(3), Z = 2. Crystal data for 2: space group P2(1)/c, a = 7.9544(17), b = 21.579(4), c = 5.0243(10) A, beta = 105.332(3) degrees , V = 831.7(3) A(3), Z = 2. Crystal data for 3: space group P2(1)/c, a = 4.7793(11), b = 15.319(3), c = 8.6022(19) A, beta = 97.156(4) degrees , V = 624.9(2) A(3), Z = 4. Magnetic measurements reveal that dominant antiferromagnetic interactions are propagated between the copper centers in compounds 1-3. For 3, spin canting is observed with a ferromagnetic transition occurring at 9 K.     

Heteroatomic deltahedral clusters of main-group elements: synthesis and structure of the Zintl ions [In4Bi5]3-, [InBi3]2-, and [GaBi3]2-

Reported are the first heteroatomic deltahedral Zintl ions made of elements differing by more than one group, indium or gallium and bismuth. Nine-atom clusters [In4Bi5]3- are characterized in two different compounds, (Na-crypt)3[In4Bi5] (4, P2(1)/n, a = 23.572(6) A, b = 15.042(4) A, c = 24.071(4) A, beta = 106.00(3) degrees, Z = 4) and (K-crypt)6[In4Bi5][In4Bi5].1.5en.0.5tol (5, P2(1)/c, a = 28.532(2) A, b = 23.707(2) A, c = 28.021(2) A, beta = 93.274(4) degrees, Z = 4). Tetrahedra of [InBi3]2- or [GaBi3]2- are found in (K-crypt)2[InBi3].en (1, P2(1), a = 12.347(4) A, b = 20.884(4) A, c = 12.619(7) A, beta = 119.02(4) degrees, Z = 2) and in the isostructural (Rb-crypt)2[InBi3].en (2, a = 12.403(8) A, b = 20.99(1) A, c = 12.617(9) A, beta = 118.83(4) degrees) and (K-crypt)2[GaBi3].en (3, a = 12.324(5) A, b = 20.890(8) A, c = 12.629(5) A, beta = 118.91(3) degrees). All compounds are crystallized from ethylenediamine/crypt solutions of precursors with nominal composition "A5E2Bi4" where A = Na, K, or Rb and E = Ga or In. The cluster in 4 is a well-ordered monocapped square antiprism with the four indium atoms occupying the five-bonded positions. Compound 5 contains two independent [In4Bi5]3- clusters; one is the same as the cluster in 4, while the other is a tricapped trigonal prism with two elongated prismatic edges. All compounds are EPR-silent and therefore diamagnetic.     

Synthesis and crystal structure of lithium beryllium deuteride Li2BeD4

Single-phase ternary deuteride Li(2)BeD(4) was synthesized by a high-pressure high-temperature technique from LiD and BeD(2). The crystal structure of Li(2)BeD(4) was solved from X-ray and neutron powder diffraction data. The compound crystallizes in the monoclinic space group P2(1)/c with lattice parameters a = 7.06228(9) A, b = 8.3378(1) A, c = 8.3465(1) A, beta =93.577(1) degrees, and Z = 8. Its structure contains isolated BeD(4) tetrahedra and Li atoms that are located in the structure interstices. Li(2)BeD(4) does not undergo any structural phase transitions at temperatures down to 8 K.     

Strontium selenogermanate(III) and barium selenogermanate(II,IV): synthesis, crystal structures, and chemical bonding

The new selenogermanates Sr2Ge2Se5 and Ba2Ge2Se5 were synthesized by heating stoichiometric mixtures of binary selenides and the corresponding elements to 750 degrees C. The crystal structures were determined by single-crystal X-ray methods. Both compounds adopt previously unknown structure types. Sr2Ge2Se5 (P2(1)/n, a = 8.445(2) A, b = 12.302 A, c = 9.179 A, beta = 93.75(3) degrees, Z = 4) contains [Ge4Se10]8- ions with homonuclear Ge-Ge bonds (dGe-Ge = 2.432 A), which may be described as two ethane-like Se3Ge-GeSeSe2/2 fragments sharing two selenium atoms. Ba2Ge2Se5 (Pnma, a = 12.594(3) A, b = 9.174(2) A, c = 9.160(2) A, Z = 4) contains [Ge2Se5]4- anions built up by two edge-sharing GeSe4 tetrahedra, in which one terminal Se atom is replaced by a lone pair from the divalent germanium atom. The alkaline earth cations are arranged between the complex anions, each coordinated by eight or nine selenium atoms. Ba2Ge2Se5 is a mixed-valence compound with GeII and GeIV coexisting within the same anion. Sr2Ge2Se5 contains exclusively GeIII. These compounds possess electronic formulations that correspond to (Sr2+)2(Ge3+)2(Se2-)5 and (Ba2+)2- Ge2+Ge4+(Se2-)5. Calculations of the electron localization function (ELF) reveal clearly both the lone pair on GeII in Ba2Ge2Se5 and the covalent Ge-Ge bond in Sr2Ge2Se5. Analysis of the ELF topologies shows that the GeIII-Se and GeIV-Se covalent bonds are almost identical, whereas the GeII-Se interactions are weaker and more ionic in character.     

Synthesis, structure, and infrared spectroscopy of the first Np5+ neptunyl silicates, Li6(NpO2)4(H2Si2O7)(HSiO4)2(H2O)4 and K3(NpO2)3(Si2O7)

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.     

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).     

Structural influences of organonitrogen ligands on vanadium oxide solids. Hydrothermal syntheses and structures of the terpyridine vanadates [V2O4(terpy)2]3[V10O28], [VO2(terpy)][V4O10], and [V9O22(terpy)3

Hydrothermal reactions of the V2O5/2,2':6':2"-terpyridine/ZnO/H2O system under a variety of conditions yielded the organic-inorganic hybrid materials [V2O4(terpy)2]3[V10O28].2H2O (VOXI-10), [VO2(terpy)][V4O10] (VOXI-11), and [V9O22(terpy)3] (VOXI-12). The structure of VOXI-10 consists of discrete binuclear cations [V2O4(terpy)2]2+ and one-dimensional chains [V10O28]6-, constructed of cyclic [V4O12]4- clusters linked through (VO4) tetrahedra. In contrast, the structure of VOXI-11 exhibits discrete mononuclear cations [VO2(terpy)]1+ and a two-dimensional vanadium oxide network, [V4O10]1-. The structure of the oxide layer is constructed from ribbons of edge-sharing square pyramids; adjacent ribbons are connected through corner-sharing interactions into the two-dimensional architecture. VOXI-12 is also a network structure; however, in this case the terpy ligand is incorporated into the two-dimensional oxide network whose unique structure is constructed from cyclic [V6O18]6- clusters and linear (V3O5(terpy)3) moieties of corner-sharing vanadium octahedra. The rings form chains through corner-sharing linkages; adjacent chains are connected through the trinuclear units. Crystal data: VOXI-10, C90H70N18O42V16, triclinic P1, a = 12.2071(7) A, b = 13.8855(8) A, 16.9832(10) A, alpha = 69.584(1) degrees, beta = 71.204(1) degrees, gamma = 84.640(1) degrees, Z = 1; VOXI-11, C15H11N3O12V5, monoclinic, P2(1)/n, a = 7.7771(1) A, b = 10.3595(2) A, c = 25.715(4) A, beta = 92.286(1) degrees, Z = 4; VOXI-12, C45H33N9O22V9, monoclinic C2/c, a = 23.774(2) A, b = 9.4309(6) A, c = 25.380(2) A, beta = 112.047(1) degrees, Z = 4.     

Synthesis and characterization of (R-C5H14N2)2[Ga4(C2O4)(H2PO4)2(PO4)4].2H2O, a layered gallium phosphatooxalate containing a chiral amine

The first metal phosphatooxalate containing a chiral amine, (R-C5H14N2)2[Ga4(C2O4)(H2PO4)2(PO4)4].2H2O, has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction and 31P MAS NMR spectroscopy. It crystallizes in the monoclinic space group P2(1) (No. 4) with a = 8.0248(4) A, b = 25.955(1) A, c = 9.0127(5) A, beta = 100.151(1) degrees, and Z = 2. The structure consists of GaO6 octahedra and GaO4 tetrahedra connected by coordinating C2O4(2-) and phosphate anions to form anionic sheets in the ac plane with charge-compensating diprotonated R-2-methylpiperazinium cations and water molecules between the layers. There is a good correlation between the NMR spectrum and the structure.     

Formation of one-, two-, and three-dimensional open-framework zinc phosphates in the presence of a tetramine

Five new open-framework zinc phosphates, encompassing the entire hierarchy of open-framework structures, have been synthesized hydrothermally in the presence of triethylenetetramine. The structures include one-dimensional ladders, two-dimensional layers, and three-dimensional structures as well as a zinc phosphate where the amine acts as a ligand. [C6N4H22]0.5[Zn(HPO4)2] (I): monoclinic, space group P2(1)/c (no. 14), a = 5.2677(1) A, b = 13.3025(1) A, c = 14.7833(1) A, beta = 96.049 degrees, Z = 4. [C6N4H22]0.5[Zn2(HPO4)3] (II): triclinic, space group P1 (no. 2), a = 7.515(1) A, b = 8.2553(1) A, c = 12.911(1) A, alpha = 98.654(1) degrees, beta = 101.274(1) degrees, gamma = 115.791(1) degrees, Z = 2. [C6N4H22]0.5[Zn2P2O8] (III): triclinic, space group P1 (no. 2), a = 8.064(1) A, b = 8.457(1) A, c = 9.023(1) A, alpha = 111.9(1) degrees, beta = 108.0(1) degrees, gamma = 103.6(1) degrees, Z = 2. [C6N4H22]0.5[Zn3(PO4)2(HPO4)] (IV): triclinic, space group P1 (no. 2), a = 5.218(1) A, b = 8.780(1) A, c = 16.081(1) A, alpha = 89.3(1) degrees, beta = 83.5(1) degrees, gamma = 74.3(1) degrees, Z = 2. [C6N4H20]0.5[Zn4P4O16] (V): monoclinic, space group P2(1)/c (no. 14), a = 9.219(1) A, b = 15.239(1) A, c = 10.227(1) A, beta = 105.2(1), Z = 4. The structure of I is composed of ZnO4 and HPO4 tetrahedra, which are edge-shared to form four-membered rings, which, in turn, form a one-dimensional chain (ladder). In II, these ladders are fused into a layer. The structures of III and IV comprise networks of ZnO4 and PO4 tetrahedra forming three-dimensional architectures. In V, the amine molecule coordinates to the Zn and acts as a pillar supporting the zinc phosphate layers, which possess infinite Zn-O-Zn linkages. The 16-membered one-dimensional channel in IV and the ZnO3N pillar, along with infinite Zn-O-Zn linkages in V, are novel features. The structure of the open-framework zinc phosphates is found to depend sensitively on the relative concentrations of the amine and phosphoric acid, with high concentrations of the latter favoring structures with lower dimensions.