Highly Kinked Uranyl Chromate Nitrate Layers in the Crystal Structures of A[(UO2)(CrO4)(NO3)] (A = K,Rb)

Two first uranyl chromate nitrates, K[(UO₂)(CrO₄)(NO₃)] ( 1 ) and Rb[(UO₂)(CrO₄)(NO₃)] ( 2 ), were prepared by solid‐state reactions and characterized by electron microprobe analysis and single‐crystal X‐ray diffraction. The compounds are isotypic [ 1 : monoclinic, P2₁/c, a = 9.881(5), b = 7.215(4), c = 14.226(6) Å, β = 124.85(3)°, V = 832.3(7) ų; 2 : monoclinic, P2₁/c, a = 9.804(1), b = 7.359(1), c = 14.269(1) Å, β = 122.048(4), V = 872.6(1) ų]. The structures of 1 and 2 are based upon the complex [(UO₂)(CrO₄)(NO₃)]^– layers with unprecedented structural topology, which consist of the UrO₃NO₃ units linked through CrO₄ tetrahedra. The resulted kinked layer can be divided into chains arranged in the ladder fashion. The layers are parallel to (100) and are linked by A⁺ (A = K, Rb) cations located between the layers.     

Thermodynamic Properties of the MZr2(PO4)3 (M=Na,K, Rb or Cs) Compounds

The enthalpies of the solution of MZr₂(PO₄)₃(M=Na, K, Rb or Cs) compounds have been measured by the help of a differential automatic isothermal Calvet calorimeter and the standard enthalpies of formation have been derived. The temperature dependencies of the standard heat capacity of the samples of crystalline NaZr₂(PO₄)₃ and CsZr₂(PO₄)₃ were studied between 7 and 340 K in an automatic adiabatic vacuum calorimeter. The main thermodynamic functions H ⁰(T)–H ⁰(0), S ⁰(T) andG ⁰(T)–H ⁰(0) have been determined. The Gibbs energies of formation of the NaZr₂(PO₄)₃and CsZr₂(PO₄)₃ at 298.15 K were calculated on the basis of these experimental data and the enthalpy of formation data. Qualitative explanations for the results observed were presented. This revised version was published online in July 2006 with corrections to the Cover Date.     

ASb2(SO4)2(PO4) (A = H3O+, K,Rb): Layered Structure Containing Ordered Sulfate and Phosphate Anions

Three compounds ASb₂(SO₄)₂(PO₄) (A = H₃O⁺, K, Rb) were obtained from the reactions of Sb₂O₃, A₂CO₃ (A = Li, Rb) or K₂SO₄ and NH₄H₂PO₄ in H₂SO₄ (98 %) at 220–250 °C. Their structures were determined by single‐crystal X‐ray diffraction. All compounds crystallize in the triclinic space group P$\bar{1}$ (no.2) and are isostructural. The crystal structures consist of two‐dimensional ²_∞[Sb₂(SO₄)₂(PO₄)]^– anionic layers and alkali cations, which are located between anionic layers. The anionic layers are composed of [SbO₄] ψ‐trigonal bipyramids, [SbO₅] ψ octahedra, [SO₄] tetrahedra, and [PO₄] tetrahedra. All compounds are characterized by solid state UV/Vis/NIR diffuse reflectance spectra, FT‐IR spectroscopy, and Raman spectroscopy.     

Mechanochemical Synthesis and Characterization of Alkaline Earth Metal Terephthalates: M(C8H4O4)·nH2O (M = Ca,Sr, Ba)

The mechanochemical synthesis offers an easy access to obtain alkaline earth metal terephthalates M(C₈H₄O₄) · nH₂O (M = Ca, Sr, Ba). In the presented study we describe for the first time the mechanochemical synthesis of powders of Ca(C₈H₄O₄) · 3H₂O, Ca(C₈H₄O₄), Sr(C₈H₄O₄) · H₂O, and Ba(C₈H₄O₄), which so far were only synthesized as single crystals from aqueous solutions or by reactions in an autoclave. Furthermore, a new hydrate Ba(C₈H₄O₄) · 2(1.5)H₂O, not described so far in the literature, was prepared. All compounds were characterized by X‐ray powder diffraction, thermal analysis, elemental analysis, FT‐IR, and MAS NMR spectroscopic measurements.     

K2M(III)2(M(VI)O4)(PO4)2 (M(III) = Fe, Sc; M(VI) = Mo, W), novel members of the lagbeinite-related family: synthesis, structure, and magnetic properties

The possibility of PO(4)(3-) for MoO(4)(2-) partial substitution in the langbeinite framework has been studied by exploration of the K-Fe(Sc)-Mo(W)-P-O systems using the high-temperature solution method. It was shown that 1/3PO(4)(3-) for MoO(4)(2-) substitution leads to formation of three novel compounds K(2)Fe(MoO(4))(PO(4))(2), K(2)Sc(MoO(4))(PO(4))(2), and K(2)Sc(WO(4))(PO(4))(2) with slightly increased lattice parameters and significant distortion of the anion tetrahedra without structure changes. In contrast, the antiferromagnetic structure is modified by substitution in the low-temperature region. The structural peculiarities are discussed in light of bond-valence sums calculations.     

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.     

Structure,infrared and Raman spectroscopic studies of newly synthetic AII(SbV0.50FeIII0.50)(PO4)2 (ABa,Sr, Pb) phosphates with yavapaiite structure

The synthesis and structural study of three new A^II(Sb^V_0.5Fe^III_0.5)(PO₄)₂ (ABa, Sr, Pb) phosphates belonging to the ASbFePO system were reported here for the first time. Structures of [Ba], [Sr] and [Pb] compounds, obtained by solid state reaction in air atmosphere, were determined at room temperature from X-ray powder diffraction using the Rietveld method. Ba^II(Sb^V_0.5Fe^III_0.5)(PO₄)₂ features the yavapaiite-type structure, with space group C2/m, Z = 2 and a = 8.1568(4) Å; b = 5.1996(3) Å c = 7.8290(4) Å; β = 94.53(1)°. A^II(Sb^V_0.5Fe^III_0.5)(PO₄)₂ (ASr, Pb) compounds have a distorted yavapaiite structure with space group C2/c, Z = 4 and a = 16.5215(2) Å; b = 5.1891(1) Å c = 8.0489(1) Å; β = 115.70(1)° for [Sr]; a = 16.6925(2) Å; b = 5.1832(1) Å c = 8.1215(1) Å; β = 115.03(1)° for [Pb]. Raman and Infrared spectroscopic study was used to obtain further structural information about the nature of bonding in selected compositions.     

A Novel Expansion Mode of Polyoxovanadate Clusters: Synthesis,Crystal Structure and Properties of {[Cu(H2O)(C5H14N2)2]2[V16O38(Cl)]}·4(C5H16N2)

The new polyoxovanadate (POV) compound {[Cu(H₂O)(C₅H₁₄N₂)₂]₂[V₁₆O₃₈(Cl)]} · 4(C₅H₁₆N₂) was synthesized under solvothermal conditions and crystallizes in the tetragonal space group I4₁/amd with a = 13.8679(6), c = 45.558(2) Å, V = 8761.7(7) ų. The central structural motif is a {V₁₆O₃₈(Cl)} cluster constructed by condensation of 16 square‐pyramidal VO₅ polyhedra. The cluster hosts a central Cl^– anion. According to valence bond sum calculations, chemical analysis and magnetic properties the cluster anion may be formulated as [V₁₅^IVV^VO₃₈(Cl)]^12–, i.e., only one vanadium atom is not reduced. To the best of our knowledge this is the first reported {V₁₆O₃₈(X)} cluster in this V^IV:V^V ratio. The presence of the two different vanadium oxidation states is clearly seen in the IR spectrum. An unusual and hitherto never observed structural feature is the binding mode between the [Cu(H₂O)(C₅H₁₄N₂)₂]²⁺ complexes and the [V₁₅^IVV^VO₃₈(Cl)]^12– anion. The Cu²⁺ ion binds to a μ₂‐O atom of the cluster anion whereas in all other transition metal complex‐augmented POVs bonding between the transition metal cation and the anion occurs through terminal oxygen atoms of the POV. The magnetic properties are dominated by strong antiferromagnetic exchange interactions between the V⁴⁺ d¹ centers, whereas the Cu²⁺ d⁹ cations are magnetically decoupled from the cluster anion. Upon heating, the title compound decomposes in a complex fashion.     

A Novel Layered Complex with Rhomboidal Channels： Hydrothermal Synthesis, Crystal Structure, and Properties of Cu （4,4′-bipy）2（H2PO4）2（H2O）2（bipy=bipyridine）

The combination of both 4,4′-bipyridine(4,4′-bipy) and dihydrogen phosphate anion ligands with copper(Ⅱ) results in the formation of a novel layered compound Cu(4,4′-bipy)₂(H₂PO₄)₂(H₂O)₂. The crystal structure comprises discrete neutral Cu(4,4′-bipy)₂(H₂PO₄)₂(H₂O)₂ units. The copper atom, located on the crystallographic twofold axis, is coordinated with two nitrogen atoms of terminal 4,4′-bipy ligands and two water molecules at the equatorial positions, and two dihydrogen phosphate oxygen atoms at the axial positions, forming an elongated octahedron. The complex is a two-dimensional distorted rhomboidal network possessing two kinds of rhomboids with dimensions of ca. 1.6792 nm×0.3203 nm and 1.2778 nm×0.3198 nm, respectively. The two-dimensional networks are stacked parallelly on each other along c-axis to give an extended three-dimensional channel network with an interlayer distance of ca. 0.5030 nm. Crystal data: triclinic, space group P1, a=1.0253(2) nm, b=1.4501(3) nm, c=0.79715(16) nm, α=97.91(3)°, β=90.99(3)°, γ=85.54(3)°, V=1.1703(4) nm³, Z=2, R=0.0892, wR=0.2451.     

Crystal Structure of a Novel Complex Na_4[Y(PDC)_2(BTC)]·5H_2O with One-Dimensional Helical Network Structure (H2PDC = 2,6-Pyridinedicarboxylic acid)( H_3BTC = 1,3,5-Benzenetricarboxylic acid )

1 INTRODUCTION The assembly of coordination networks is a field of increasing interest[1~4]. Research along this line is induced by the idea that coordination networks have potential technological applications such as optoele- ctronic devices and microporous materials for shape and size separation and catalysis[5~7]. In this paper, there has been current interest in using polycarboxy- late as anion linking groups to support stable poly- meric coordination open frameworks with transition m…     

RBa2Cu4O8(R=Dy, Ho, Er, Tm, Yb)和Y2Ba4Cu7O14.3的化学键参数计算

使用复杂晶体上化学键理论计算了RBa2Cu4O8(R=Dy,Ho,Er,Tm,Yb)和Y2Ba4Cu7O14.3的化学键参数。结果表明,CuO1链上的CuO键共价性大于它们在CuO2面的共价性,当金属元素与氧形成五配位时,其共价性的数值大于这些元素在六配位时的情形。     

Synthesis, crystal structure from single-crystal and powder X-ray diffraction data, and thermal behavior of mixed potassium lanthanide squarates: thermal transformations of layered [Ln(H2O)6]K(H2C4O4)(C4O4)2 into pillared LnK(C4O4)2 (Ln = Y, La, Gd, Er)

A new series of mixed potassium and rare-earth squarates, [Ln(H(2)O)(6)]K(H(2)C(4)O(4))(C(4)O(4))(2) (Ln = Y, La, Gd, Er), has been synthesized and structurally characterized from single-crystal X-ray diffraction and spectroscopic analyses. The yttrium-based compound crystallizes with a monoclinic symmetry, space group C2/c [a = 8.3341(2) A, b = 37.7094(9) A, c = 11.7195(3) A, beta = 90.3959(9) degrees , V = 3683.1(2) A(3), Z = 8]. The structure is built from layers maintained together via hydrogen bonds. Within a layer, squarate ligands act as linkers between lanthanide and potassium cations. The thermal decomposition of the precursors has been studied by powder thermodiffractometry and thermal analyses. It is shown that crystalline intermediate phases are formed during the degradation. Among them, unprecedented mixed anhydrous squarates, LnK(C(4)O(4))(2), could be isolated. The crystal structure of the Y compound has been solved ab initio from X-ray powder diffraction data, using direct-space methods [a = 6.2010(5) A, c = 11.639(1) A, V = 447.55 A(3), Z = 2]. The structure consists of layers of edge-sharing YO(8) and KO(8) antiprisms, pillared by mu(8)-squarate groups. The end of the precursor decomposition is marked by the formation of cubic sesquioxides Ln(2)O(3), including lanthanum oxide.     

Einfache Trithio- und Perthiocarbonatokomplexe mit interessanter Koordinationschemie: [E(CS3)2]2− (E = Sn,Zn, Cd), [E(CS3)3]3− (E = As,Sb, Bi,Co), {Cu(CS3)−}∞ und [Zn(CS4)2]2−

Simple Trithio- and Perthiocarbonato Complexes with Interesting Bond Properties: [E(CS₃)₂]^2? (E = Sn, Zn, Cd), [E(CS₃)₃]^3? (E = As, Sb, Bi, Co), {Cu(CS₃)^?}_∞ and [Zn(CS₄)₂]^2? By reactions of potassium trithiocarbonate ( 1 ) with solutions of zinc(II)- acetylacetonate, cadmium(II)-chloride, tin(II)-chloride, arsenic(III)-sulfide (suspension), antimony(III)-chloride, bismuth(III)-chloride and copper(II)-chloride in dimethyl sulfoxide, as well as of trisodium hexanitrito cobaltate(III) in water, and the precipitation of the complexes with an aqueous solution of tetraphenylphosphonium chloride the compounds (PPh₄)₂[Zn(CS₃)₂] ( 2 ), (PPh₄)₂[Cd(CS₃)₂] ( 3 ), (PPh₄)₂[Sn(CS₃)₂] ( 4 ), (PPh₄)₃[As(CS₃)₃] ( 5 ), (PPh₄)₃[Sb(CS₃)₃] ( 6 ), (PPh₄)₃[Bi(CS₃)₃] ( 7 ), (PPh₄)₃[Co(CS₃)₃] ( 8 ) and (PPh₄)Cu(CS₃) ( 9 ) have been isolated. (PPh₄)₂[Zn(CS₄)₂] · CH₃NO₂ ( 10 ) has been prepared by heating a solution of 2 in nitromethane to 60--70°C in presence of air. The reaction of 1 in dimethyl sulfoxide with an aqueous tetraphenylphosphonium chloride solution in presence of oxygen leads to (PPh₄)₂[C₂S₆] ( 11 ). The compounds have been characterized by spectroscopical studies (IR, Raman, UV/Vis, ¹¹³Cd/⁵⁹Co-NMR), magnetic susceptibility measurements, powder diffractometry, elemental analyses and single crystal X-ray structure analysis ( 4 – 7 , 10 and 11 ). The difficult growing of single crystals has been reported in detail. For crystal data see Inhaltsübersicht.     

新型邻菲咯啉镁(II)配合物[Mg(H_2O)_4(phen)](phen)[C_6H_4(COO)_2]·H_2O的水热合成和晶体结构

合成了新型邻菲咯啉镁(II)配合物 [Mg(H2O)4(phen)](phen)[C6H4(COO)2]?H2O, 并对其进行了元素分析、IR、TG、X-射线衍射等表征。单晶衍射结果表明, 该配合物晶体属单斜晶系, 空间群为 P21/c, 晶胞参数:a = 11.873(2), b = 31.992(6), c = 8.144(2) ?, β = 93.98(3), V = 3085.9(11)?3, Z = 4, F(000) = 1336, Dc = 1.375 g/cm3, μ(MoKα) = 0.120 mm?1。对于 6889[ Rint = 0.0264]个独立衍射点, 有 3939 个可观测点满足(I≥2σ (I)), 最终的偏离因子 R = 0.0430, wR = 0.1294。标题配合物由 1 个邻菲咯啉合镁阳离子[Mg(H2O)4(phen)]2+、1 个邻苯二甲酸根阴离子C6H4(COO)2)2–、1 个溶剂邻菲咯啉分子和 1 个结晶水分子组成。中心 Mg(II)离子为六配位, 六个配位原子形成畸变的 MgN2O4八面体构型。     

Synthesis and Structure of K[Cd(O2N‐C6H4‐NNN‐C6H4‐NO2)3], an Anionic 1, 3‐Bis(4‐nitrophenyl)triazenido Complex of Cadmium

The reaction of cadmium acetate in methanol with 1, 3‐bis(4‐nitrophenyl)triazene in THF in the presence of KOH yields K[Cd(O₂NC₆H₄NNNC₆H₄NO₂)₃] in form of hexagonal prismatic, red crystals with the trigonal space group R3¯ and a = 12.229(2), c = 48.988(10) Å and Z = 6. In the anionic cadmium complexes, which are located along the threefold axis, the Cd atoms are coordinated in a trigonal prismatic arrangement by the atoms N(1) and N(3) of three triazenido ligands. The potassium cations are coordinated icosahedrally by oxygen atoms of each one nitro group of six neighbouring anionic complexes. The Cd‐N distances are 2.376(4) and 2.350(4) Å, and the K‐O distances are in the range of 2.833(6) to 3.365(6) Å.     

Syntheses and Spectroscopic Study of Some New N‐4‐Fluorobenzoyl Phosphoric Triamides; Crystal Structures of 4‐F‐C6H4C(O)N(H)P(O)R2, R = NH‐C(CH3)3, NH‐CH2C6H5, N(CH3)(CH2C6H5)

Some new N‐4‐Fluorobenzoyl phosphoric triamides with formula 4‐F‐C₆H₄C(O)N(H)P(O)X₂, X = NH‐C(CH₃)₃ ( 1 ), NH‐CH₂‐CH=CH₂ ( 2 ), NH‐CH₂C₆H₅ ( 3 ), N(CH₃)(C₆H₅) ( 4 ), NH‐CH(CH₃)(C₆H₅) ( 5 ) were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR and Mass spectroscopy and elemental analysis. The structures of compounds 1 , 3 and 4 were investigated by X‐ray crystallography. The P=O and C=O bonds in these compounds are anti. Compounds 1 and 3 form one dimensional polymeric chain produced by intra‐ and intermolecular ‐P=O···H‐N‐ hydrogen bonds. Compound 4 forms only a centrosymmetric dimer in the crystalline lattice via two equal ‐P=O···H‐N‐ hydrogen bonds. ¹H and ¹³C NMR spectra show two series of signals for the two amine groups in compound 1 . This is also observed for the two α‐methylbenzylamine groups in 5 due to the presence of chiral carbon atom in molecule. ¹³C NMR spectrum of compound 4 shows that ²J(P,C_aliphatic) coupling constant for CH₂ group is greater than for CH₃ in agreement with our previous study. Mass spectra of compounds 1 ‐ 3 (containing 4‐F‐C₆H₄C(O)N(H)P(O) moiety) indicate the fragments of amidophosphoric acid and 4‐F‐C₆H₄CN⁺ that formed in a pseudo McLafferty rearrangement pathway. Also, the fragments of aliphatic amines have high intensity in mass spectra.