Synthesis and Structure of a Three‐dimensional Organically Templated Zinc Ethylenediphosphonate, [NH3(CH2)2NH3][Zn3{O3P(CH2)2}4]

A hydrothermal reaction of a mixture of ZnO, HCl, ethylenediphosphonic acid, ethylenediamine, acetic acid in a water, THF mixture gave rise to a new three‐dimensional zinc ethylenediphosphonate, [NH₃(CH₂)₂NH₃][Zn₃{O₃P(CH₂)₂}₄], I . The structure, determined by single crystal X‐ray diffraction, (monoclinic, space group = C2/c, a = 16.9948(14), b = 6.7383(6), c = 16.8886(14)Å, β = 1113.568(1)°, V = 1772.7(3)ų, Z = 4, R₁ = 0.0227, wR₂ = 0.0601), consists of a network of strictly alternating ZnO₄ and PO₃C tetrahedral units linked through their vertices forming the three‐dimensional structure. The amine molecules occupy the middle of the 8‐membered channels and interact with the framework through the hydrogen bonds. Unlike other zinc diphosphonates, I appear to have close similarity to zinc phosphate structures reported in the literature. To our knowledge, this is the first three‐dimensional zinc diphosphonate prepared in the presence of an organic amine molecule.     

Synthesis and Structure of a One‐Dimensional Aluminum Phosphate, [NH3(CH2)2NH2(CH2)3NH3]3+ [Al(PO4)2]3—

A one‐dimensional aluminum phosphate, [NH₃(CH₂)₂NH₂(CH₂)₃NH₃]³⁺ [Al(PO₄)₂]^3—, has been synthesized hydrothermally in the presence of N‐(2‐Aminoethyl‐)1, 3‐diaminopropane (AEDAP) and its structure determined by single crystal X‐ray diffraction. Crystal data: space group = Pbca (no. 61), a = 16.850(2), b = 8.832(1), c = 17.688(4)Å, V = 2632.4(2)ų, Z = 8, R₁ = 0.0389 [5663 observed reflections with I > 2σ(I)]. The structure consists of anionic [Al(PO₄)₂]^3— chains built up from AlO₄ and PO₄ tetrahedra, in which all the AlO₄ vertices are shared and each PO₄ tetrahedron possesses two terminal P=O linkages. The cations, which balances the negative charge of the chains, are located in between the chains and interact with the oxygen atoms through strong N—H···O hydrogen bonds. Additional characterization of the compound by powder XRD and MAS‐NMR has also been performed and described.     

A novel chain-like molybdenum phosphate: hydrothermal synthesis,crystal structure and characterization of [NH3(CH2CH2)2NH3]3[NH3(CH2CH2)2NH2]-Na5[Mo6O12(OH)3(PO4)(HPO4)3]2·4H2O

A novel organic/inorganic hybrid molybdenum phosphate, [NH₃(CH₂CH₂)₂NH₃]₃[NH₃(CH₂CH₂)₂NH₂]Na₅-[Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃]₂·4H₂O (1), involving molybdenum presented in V oxidation, has been hydrothermally prepared and characterized by elemental analysis, i.r., u.v.–vis., x.p.s., t.g. and single crystal X-ray diffraction. The structure of the title compound (1) may be considered to consist of two [Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃] units bonded together with NaO₆ octahedra, forming dimers. Further, these dimers connect with each other through four Na⁺ cations as bridges, giving rise to novel one-dimensional chain-like skeleton. Piperazines exist among inorganic chains acting as charge balancing cations.     

First Characterization of an Extended Ammonium‐Ammonia Complex [{NH4(NH3)4}+(μ‐NH3)2] in the Crystal Structure of [NH4(NH3)4][Co(C2B9H11)2] · 2 NH3

The compound [NH₄(NH₃)₄][Co(C₂B₉H₁₁)₂] · 2 NH₃ ( 1 ) was prepared by the reaction of Na[Co(C₂B₉H₁₁)₂] with a proton‐charged ion‐exchange resin in liquid ammonia. The ammoniate 1 was characterized by low temperature single‐crystal X‐ray structure analysis. The anionic part of the structure consists of [Co(C₂B₉H₁₁)₂]^‐ complexes, which are connected via C‐H···H‐B dihydrogen bonds. Furthermore, 1 contains an infinite equation/tex2gif-stack-2.gif[{NH₄(NH₃)₄}⁺(μ‐NH₃)₂] cationic chain, which is formed by [NH₄(NH₃)₄]⁺ ions linked by two ammonia molecules. The N‐H···N hydrogen bonds range from 1.92 to 2.71Å (DHA = Donor···Acceptor angles: 136‐176°). Additional N‐H···H‐B dihydrogen bonds are observed (H···H: 2.3‐2.4Å).     

Vergleich der Kristallstrukturen der Tetraammoniakate von Lithiumhalogeniden,LiBr·4NH3 und LiI·4NH3, mit der Struktur von Tetramethylammoniumiodid,N(CH3)4I

A Comparison of the Crystal Structures of the Tetraammoniates of Lithium Halides, LiBr·4NH₃ and LiI·4NH₃, with the Structure of Tetramethylammonium Iodide, N(CH₃)₄I Crystals of the tetraammoniates of LiBr and LiI sufficient in size for X‐ray structure determinations were obtained by slow evaporation of NH₃ at room temperature from a clear solution of the halides in liquid ammonia. The compounds crystallize in the space group Pnma (No. 62) with four formula units in the unit cell: LiBr·4NH₃: a = 11.947(5)Å, b = 7.047(4)Å, c = 9.472(3)Å LiI·4NH₃: a = 12.646(3)Å, b = 7.302 (1)Å, c = 9.790(2)Å For N(CH₃)₄I the structure was now successfully solved including the hydrogen positions of the methyl groups. N(CH₃)₄I: P4/nmm (No. 129), Z = 2, a = 7.948(1)Å, c = 5.738(1)Å The ammoniates of LiBr and LiI crystallize isotypic in a strongly distorted arrangement of the CsCl motif. Even N(CH₃)₄I has an CsCl‐like structure. Both structure types differ mainly in their orientation of the [Li(NH₃)₄]⁺ — resp. [N(CH₃)₄]⁺ — cations with respect to the surrounding “cube” of anions.     

Tetraammonium Diglycinyl‐octamolybdate(VI) Dihydrate, (NH4)4[(NH3CH2CO)2(Mo8O28)] · 2 H2O

The reaction of ammonium heptamolybdate with hydrazine sulfate in an aqueous solution of glycine at room temperature yielded colorless crystals of (NH₄)₄[(NH₃CH₂CO)₂(Mo₈O₂₈)] · 2 H₂O. The crystal is monoclinic, space group C2/c (no. 15), a = 17.234 Å, b = 10.6892 Å, c = 18.598 Å, β = 108.280°, V = 3253.2 ų, Z = 4. The crystal structure contains ammonium cations and isolated octamolybdate(4–) anions, [(NH₃CH₂CO)₂(Mo₈O₂₈)]^4–, with two zwitterionic glycine molecules as ligands.     

Spezielle Alkylammoniumhexachlorometallate. I. Kristallisationsverhalten und Kristallstruktur von Diethylentriammoniumhexachlororhodat, [H3N(CH2)2NH2(CH2)2NH3][RhCl6]

Alkylammonium Hexachlorometallates. I. Crystallization Properties and Crystal Structure of Diethylenetriammonium Hexachlororhodate, [H₃N(CH₂)₂NH₂(CH₂)₂NH₃][RhCl₆] The reaction of RhCl₃ · 3H₂O with diethylenetriamine in 12 m hydrochloric acid yielded diethylenetriammonium hexachlororhodate [H₃N(CH₂)₂NH₂(CH₂)₂NH₃][RhCl₆] ( 1 ). Dark red single crystals of the compound were grown under hydrothermal conditions at a temperature interval of 180°C to 125°C in closed glass ampoules over several weeks (space group C2/c, a = 30.956(4) Å, b = 7.371(2) Å, c = 12.9736(15) Å, β = 113.787(11)°, Z = 8, 2385 reflections with I > 0, wR²(obs.) = 0.0279, R¹(I > 2σ(I)) = 0.0271). The crystal structure is determined by a complex framework of hydrogen bonds between the hexachlororhodate anions and the diethylenetriammonium cations.     

Synthese,Kristallstruktur und Magnetismus von [(CH3)2NH2][PrCl4(H2O)2]

Preparation, Crystal Structure, and Magnetism of [(CH₃)₂NH₂][PrCl₄(H₂O)₂] The complex water containing chloride [(CH₃)₂NH₂][PrCl₄(H₂O)₂] has been prepared for the first time and the crystal structure has been determined from single crystal X‐ray diffraction data. The compound crystallizes orthorhombically in the space group Cmca (Z = 8) with a = 1796.6(2) pm, b = 940.7(1) pm, and c = 1238.4(2) pm. The anionic part of the structure is built up by chains of edge‐connected trigondodecahedra [PrCl₆(H₂O)₂]^3– according to [PrCl_4/2Cl₂(H₂O)₂]^–, which are held together by dimethylammonium cations ([(CH₃)₂NH₂]⁺). In order to study the interactions between the praseodymium cation (Pr³⁺) and the ligands magnetic measurements were carried out. The magnetic data were interpreted by ligand field calculations applying the angular overlap model.     

Hydrothermal synthesis and structural determination of a three-dimensional microporous iron(III)phosphate: [H3N(CH2)4NH3]3[Fe8(HPO4)12(PO4)2(H2O)6]

A new microporous iron (III) phosphate, [H₃N(CH₂)₄NH₃]₃[Fe₈(HPO₄)₁₂(PO₄)₂(H₂O)₆], has been prepared using low temperature hydrothermal methods and characterized by single-crystal X-ray diffraction, EDAX, infrared spectroscopy, thermogravimetric analysis and bond valence sums. The title compound crystallizes as light pink hexagonal-shaped tabs in the centrosymmetric hexagonal space group 3¯ (No.147) with a = b = 13.495(2) Å, c = 9.396(2) Å, V = 1481.9(4) ų and Z = 4 with R/R_w = 0.044/0.048. The compound exhibits a complicated three-dimensional microporous structure with quaternary ammonium ions acting as a template for the framework. It is similar to previously reported [HN(CH₂CH₂)₃NH]₃[Fe₈(HPO₄)₁₂(PO₄)₂(H₂O)₆].     

Crystallographic report: A two‐dimensional zinc phosphate framework: [H3N(CH2)3NH3]0.5[Zn2(PO4)(HPO4)]

The two‐dimensional zinc phosphate [H₃N(CH₂)₃NH₃]_0.5[Zn₂(PO₄)(HPO₄)], has been synthesized hydrothermally using 1,3‐diaminopropane as the template. Its structure contains an inorganic framework with three‐, four‐, or six‐membered rings, built from PO₄, PO₃(OH) and ZnO₄ tetrahedral moieties sharing vertexes. The protonated 1,3‐diaminopropane molecules interact with the framework through hydrogen bonds. Copyright © 2004 John Wiley & Sons, Ltd.     

Syntheses,Structures and Magnetic Properties of Two Mixed‐Valent Disc‐like Hepta‐nuclear Compounds of [FeIIFeIII6(tea)6](ClO4)2 and [MnII3MnIII4(nmdea)6(N3)6]·CH3OH (tea = N(CH2CH2O)33−, nmdea = CH3N(CH2CH2O)22−)

Two mixed‐valent disc‐like hepta‐nuclear compounds of [Fe^IIFe^III₆(tea)₆](ClO₄)₂ ( 1Fe , tea = N(CH₂CH₂O)₃^3?) and [Mn^II₃Mn^III₄(nmdea)₆(N₃)₆]·CH₃OH ( 2Mn , nmdea = CH₃N(CH₂CH₂O)₂^2?) have been synthesized by the reaction of Fe(ClO₄)₂·6H₂O with triethanolamine (H₃tea) for the former and reaction of Mn(ClO₄)₂·6H₂O with diethanolamine (H₂nmdea) and NaN₃ for the later, respectively. 1Fe has the cationic cluster with a planar [Fe^IIFe^III₆] core consisting of one central Fe^II and six rim Fe^III atoms in hexagonal arrangement. The Fe ions are linked by the oxo‐bridges from the alcohol arms in the manner of edge‐sharing of their coordination octahedra. 2Mn is a neutral cluster with a [Mn^II₃Mn^III₄] core possessing one central Mn^II atom surrounded by six rim Mn ions, two Mn^II and four Mn^III. The structure is similar to 1Fe but involves six terminal azido ligands, each coordinate one rim Mn ion. 1Fe showed dominant antiferromagnetic interaction within the cluster and long‐range ordering at 2.7 K. The cluster probably has a ground state of low spin of S = 5/2 or 4/2. The long‐range ordering is weak ferromagnetic, showing small hysteresis with a remnant magnetization of 0.3 Nβ and a coercive field of 40 Oe. Moreover, the isofield of lines 1Fe are far from superposition, indicating the presence of significant zero–field splitting. Ferromagnetic interactions are dominant in 2Mn . An intermediate spin ground state 25/2 is observed at low field. In high field of 50 kOe, the energetically lowest state is given by the m_s = 31/2 component of the S = 31/2 multiplet due to the Zeeman effect. Despite of the large ground state, no single‐molecule magnet behavior was found above 2 K.     

Synthese und Kristallstruktur des heterobimetallischen Diorganozinndichlorids (FcN,N)2SnCl2 (FcN,N—: (η5‐C5H5)Fe{(η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2}—)

Synthesis and Crystal Structure of the Heterobimetallic Diorganotindichloride (FcN, N)₂SnCl₂ (FcN, N^—: (η⁵‐C₅H₅)Fe{η⁵‐C₅H₃[CH(CH₃)N(CH₃)CH₂CH₂NMe₂]‐2}^—) The heterobimetallic title compound [(FcN, N)₂SnCl₂] ( 1 ) was obtained by the reaction of [LiFcN, N] with SnCl₄ in the molar ratio 1:1 in diethylether as a solvent. The two FcN, N^— ligands in 1 are bound to Sn through a C‐Sn σ‐bond; the amino N atoms of the side‐chain in FcN, N^— remain uncoordinated. The crystals contain monomeric molecules with a pseudo‐tetrahedral coordination at the Sn atom: Space group P2₁/c; Z = 4, lattice dimensions at —90 °C: a = 9.6425(2), b = 21.7974(6), c = 18.4365(4) Å, β = 100.809(2)°, R1_obs· = 0.051, wR2_obs· = 0.136.     

(Carbonyl)Iron‐Selenolates: New Synthetic Methods and Reactions with Electrophiles. Crystal Structures of [(CO)6Fe2(μ‐SeR)2]; R = Me3SiCH2 and p‐O2NC6H4CH2, {(CO)6Fe2[μ‐η2‐Se,Se′‐o‐(SeCH2C6H4CH2Se)]}, and [(CO)6Fe2(μ‐SeFe(CO)2cp)2]

The reactions of Fe(CO)₅ or Fe₃(CO)₁₂ with NaBEt₃H or KB[CH(CH₃)C₂H₅]₃H, respectively and treatment of the resulting carbonylates M₂Fe(CO)₄, M = Na, K with elemental selenium in appropriate ratios lead to the formation of M₂[Fe₂(CO)₆(μ‐Se)₂]. Subsequent reactions with organo halides or the complex fragment cpFe(CO)₂⁺, cp = η⁵‐C₅H₅ afforded the selenolato complexes [Fe₂(CO)₆(μ‐SeR)₂], R = CH₂SiMe₃ ( 1 ), CH₂Ph ( 2 ), p‐CH₂C₆H₄NO₂ ( 3 ), o‐CH₂C₆H₄CH₂ ( 4 ) and cpFe(CO)₂⁺ ( 5 ) in moderate to good yields. A similar reaction employing Ru₃(CO)₁₂, Se and p‐O₂NC₆H₄CH₂Br leads to the formation of the corresponding organic diselenide. The X‐ray structures of 1 , 3 , 4 and 5 were determined and revealed butterfly structures of the Fe₂Se₂ cores. The substituents in 1 , 3  and 5 adopt different conformations depending on their steric demand. In 4 , the conformation is fixed because of the chelate effect of the ligand. The Fe–Se bond lengths lie in the range 235 to 240 pm, with corresponding Fe–Fe bond lengths of 254 to 256 pm. The ⁷⁷Se NMR data of the new complexes are discussed and compared with the corresponding data of related complexes.     

Neptunium(VI) Chromate Complex with 1,2-Diammoniopropane {H3NCH2CH(NH3)CH3}[(NpO2)2(CrO4)3(H2O)] · 3H2O: Synthesis,Crystal Structure and Properties

New neptunium(VI) complex {H₃NCH₂CH(NH₃)CH₃}[(NpO₂)₂(CrO₄)₃(H₂O)] · 3H₂O is synthesized; its crystal structure is determined and IR and near-IR absorption spectra are recorded. The crystallographic data are: a = 10.805(2) Å, b = 11.238(2) Å, c = 17.615(8) Å, space group P2₁2₁2₁, Z = 4, V = 2139(1) ų, R = 0.051, wR(F ²) = 0.109. The crystal structure of the compound is built of the anionic layers of [(NpO₂)₂(CrO₄)₃(H₂O)]^2n– _n . The {H₃NCH₂CH(NH₃)CH₃}²⁺ cations and crystallization water molecules are arranged between the layers. Coordination polyhedron of two crystallographically independent Np atoms has the shape of a pentagonal bipyramid. The equatorial plane in one Np polyhedron is formed by the oxygen atoms of four chromate ions and water molecule and by the oxygen atoms of five chromate ions in the other one.     

An A‐Site Mixed‐Ammonium Solid Solution Perovskite Series of [(NH2NH3)x(CH3NH3)1−x][Mn(HCOO)3] (x=1.00–0.67)

The A‐site mixed‐ammonium solid solutions of metal–organic perovskites [(NH₂NH₃)_x(CH₃NH₃)_1?x][Mn(HCOO)₃] (x=1.00–0.67) exhibit para‐ to ferroelectric diffuse phase transitions with lowered transition temperatures from x=1.00 to 0.67. These properties are due to the decreased framework distortion and polarization in their low temperature ferroelectric phases caused by the increased CH₃NH₃⁺ concentration.     

Synthesis,physicochemical characterization and biological activity of nano complexes of iron(III) of 3(2'‐hydroxyphenyl)‐5‐(4′‐substituted phenyl) pyrazolines and aspartic acid

Mixed ligand complexes of Iron(III) with aspartic acid and 3(2′‐hydroxy phenyl)‐5‐(4′‐substituted phenyl) pyrazolines of type [Fe(C₄O₄NH₆)₂(C₁₅H₁₂N₂OX)] and [Fe(C₄O₄NH₆)(C₁₅H₁₂N₂OX)₂], where (C₄O₄NH₆) = aspartate, (C₁₅H₁₂N₂OX) = deprotonated 3(2′‐hydroxyphenyl)‐5‐(4′‐substituted phenyl) pyrazolines (X = H, CH₃, OCH₃, Cl), have been synthesized. These newly synthesized derivatives have been physicochemically characterized by elemental analysis (C, H, N, Cl and Fe), magnetic moment data, thermogravimetric analysis, molar conductance, cyclic voltammetry, spectral analysis (UV–visible, IR, far IR and fast atom bombardment mass spectrometry). Scanning electron microscopy, transmission electron microscopy and X‐ray powder diffraction studies have been carried out for powdered samples, which show nanometric particles of these derivatives. Antibacterial and antifungal potential of free pyrazoline and some iron(III) complexes have been evaluated. Copyright © 2012 John Wiley & Sons, Ltd.     

[NH3(CH2)6NH3][P2V5O17]·3.83H2O: A new 3D Organic‐templated Vanadophosphate with Extra‐large 16‐Membered Ring Constructed from Nanosized P–O–V Wheels

A new porous 3D vanadophosphate, [NH₃(CH₂)₆NH₃][P₂V₅O₁₇] · 3.83H₂O ( 1 ) is synthesized by using NH₂(CH₂)₆NH₂ as template, and characterized by single crystal structural analysis, X‐ray diffraction, IR spectroscopy, TG analysis, and powder XRD. Single crystal analysis shows that compound 1 crystallizes in cubic shape, space group Im m with cell dimensions: a = b = c = 26.5068(8) Å, V = 18624.0(10) Å³, Z = 24. Structural refinement indicates that the inorganic framework of 1 is constructed from nanosized P–O–V wheels.     

含有NH2CH2CH2CH2NH2和o-C6H4(NH2)2配体的镍配合物的合成、结构和它们在乙烯聚合中的作用

两种镍的配合物[Ni(NH2CH2CH2CH2NH2)3]Cl2 (1)和[Ni(C6H4N2H4)2Cl2] (2)已经被合成并且通过红外和单晶X射线衍射分析对其进行了表征。在配合物1中,镍原子处于手性假八面体[NiN6]的几何构型中,它与三个1,3-丙二胺分子形成了三个六元环。在配合物2中,镍原子除了与两个o-苯二胺分子通过四个Ni-N键形成两个五元环外,它还与两个Cl原子配位形成了反式Ni-Cl2,这不同于以往报道过的镍的二胺配合物。这两个镍的配合物被MAO, MMAO或Et2AlCl活化后,对乙烯的二聚合或三聚合显示了很好的催化活性[对于配合物2,催化活性达到3.59×106 g mol-1 (Ni) h-1]。     

Synthese,Kristallstruktur und Magnetismus von [(CH3)2NH2][NdCl4(H2O)2]

Preparation, Crystal Structure, and Magnetism of [(CH₃)₂NH₂][NdCl₄(H₂O)₂] The complex water containing chloride [(CH₃)₂NH₂][NdCl₄(H₂O)₂] was prepared for the first time and the crystal structure was determined by X‐ray methods from single crystals. The compound crystallizes in the orthorhombic space group Cmca (Z = 8) with a = 1793.5(2) pm, b = 936.6(2) pm and c = 1232.8(2) pm. The anionic part of the structure is built up by chains of edge connected [NdCl_4/2Cl₂(H₂O)₂]^– trigondodecahedra. In order to study the interactions between the neodymium cation and the ligands magnetic measurements were carried out. The magnetic data were interpreted by ligand field calculations applying the angular overlap model.     

Das wasserfreie Lanthanacetat,La(CH3COO)3, und sein Precursor,NH4)3[La(CH3COO)6] · 1/2 H2O: Synthese,Strukturen, thermisches Verhalten

Anhydrous Lanthanum Acetate, La(CH₃COO)₃, and its Precursor, ·NH₄)₃[La(CH₃COO)₆] · 1/2 H₂O: Synthesis, Structures, Thermal Behaviour Single crystals of (NH₄)₃[La(CH₃COO)₆] · ½ H₂O are obtained by refluxing La₂O₃in (CH₃COO)₃ · 1.5 H₂O with an excess of NH₄CH₃COO in methanol. The crystal structure (trigonal, R3 , Z = 6, a = 1 365.0(3) pm, c = 2 360(1) pm, R = 0.088, R_w = 0.061 exhibits the coordination number of nine for La³⁺, which is surrounded by three chelating-type bidentate and three unidentate acetate groups. Characteristic are monomeric units of [La(CH₃COO)₆]^3? which are connected to a three-dimensional network by hydrogen bonds with the NH ions. Thermal decomposition consists of four steps with La(CH₃COO)₃, La₂(CO₃)₃ and La₂O₂CO₃ as intermediates and La₂O₃ as the final Product. Single crystals of La(CH₃COO)₃ are obtained from La₂O₃ in a melt of NH₄CH₃COO (molar ratio 1:12) in a sealed glass ampoule. The crystal structure (trigonal, R3 , Z = 18, a = 2 203.0(5) pm; c = 987.1(3) pm, R = 0.027, R_w = 0.023) shows the coordination number of ten for La³⁺. These are three-dimensionally connected by oxygen atoms of the acetate groups with two tetradentate double-bridging and one Z,Z-type-bridging bidentate acetate group.