Synthesis and Crystal Structure of [Ni(H2O)6][Ni(H2O)2(C4H2O4)]·4H2O

Reaction of a freshly prepared Ni(OH)_{2?2 x} (CO₃) _x ·yH₂O with maleic acid in H₂O at room temperature afforded [Ni(H₂O)₆][Ni(H₂O)₂(C₄H₂O₄)]·4H₂O, which consists of [Ni(H₂O)₆]²⁺ cations, [Ni(H₂O)₂(C₄H₂O₄)]^2? anions and lattice H₂O molecules. Ni atoms in cations are octahedrally coordinated and Ni atoms in anions are each octahedrally coordinated by bidentate chelating maleato ligands and two water molecules at trans positions. Cations and anions are interlinked by hydrogen bonds to form 1D chains, which are hexagonally arranged and connected by the lattice water molecules. When heated in a flowing argon stream, the compound decomposes, with complete dehydration being followed by dissociation of nickel maleate into NiO and maleic anhydride.     

New 1D and 2D metal oxygen connectivities in Cu(II) succinato and glutarato coordination polymers: [Cu3(H2O)2(OH)2(C4H4O4)2] · 4H2O, [Cu4(H2O)2(OH)4(C4H4O4)2] · 5H2O and [Cu5(OH)6(C5H6O4)2] · 4H2O

Two Cu(II) hydroxo succinates [Cu₃(H₂O)₂(OH)₂(C₄H₄O₄)₂]?·?4H₂O (1) and [Cu₄(H₂O)₂(OH)₄(C₄H₄O₄)₂]?·?5H₂O (2) and one Cu(II) hydroxo glutarate [Cu₅(OH)₆(C₅H₆O₄)₂]?·?4H₂O (3) have been prepared and structurally characterized by single crystal X-ray diffraction methods. They feature 1D and 2D copper oxygen connectivity of elongated {CuO₆} octahedra in “4?+?1?+?1” and “4?+?2” coordination geometries. Within 1, linear trimers of three edge-sharing {CuO₆} octahedra are connected into copper oxygen chains, which are bridged by the anti conformational succinate anions to generate 2D layers with mono terminally coordinating gauche succinate anions on both sides. The layers are assembled into a 3D framework by interlayer hydrogen bonds with lattice H₂O molecules distributed in channels. Different from 1, the principal building units in 2 are linear tetramers of four edge-sharing {CuO₆} octahedra. The tetramers are condensed into copper oxygen chains and the succinate anions interlink them into a 3D framework with triangular channels filled by lattice H₂O molecules. The {CuO₆} octahedra in 3 are edge-shared to form unprecedented 2D inorganic layers with mono terminally coordinating glutarate anions on both sides. Interlayer hydrogen bonding interactions are responsible for supramolecular assembly of the layers into a 3D framework with lattice H₂O molecules in the channels. The inorganic layers in 3 can be described as hexagonal close packing of oxygen atoms with the Cu atoms in the octahedral cavities. The title compounds were further characterized by elemental analyses, IR spectra and thermal analyses.     

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O and [La(DMSO)4(H2O)3Co(CN)6]·H2O (DMSO = Dimethylsulfoxide)

Two new bimetallic cyano-bridged complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O 1 and [La(DMSO)4(H2O)3Co(CN)6]·H2O 2 have been prepared by the ball milling reaction method and structurally characterized by X-ray single-crystal structure analyses. Crystallographic data for 1:C14H32CeFeN6O8S4, Mr = 736.67, monoclinic, space group P21/n, a = 14.952(1), b =13.7276(9), c = 15.392(1) (A), β = 108.288(1)°, V = 2999.6(4) (A)3, Z = 4, Dc= 1.631 g/cm3,μ =2.304 mm-1, F(000) = 1480, R = 0.0593 and wR = 0.1611; and those for 2: C14H32CoLaN6O8S4,Mr=738.54, monoclinic, space group P21/n, a = 14.945(3), b = 13.731(3), c = 15.300(3) (A), β=107.806(1)°, V= 2989.3(11) (A)3, Z = 4, Dc = 1.641 g/cm3,μ = 2.288 mm-1, F(000) = 1480, R =0.0383 and wR = 0.1132. In both complexes the lanthanide ion is eight-coordinated in a square antiprism arrangement, and the Fe(Ⅲ) or Co(Ⅲ) ion in a nearly regular octahedral environment.The [LnM(CN)6(DMSO)4(H2O)3]·H2O (Ln = Ce and M = Fe for 1; Ln = La and M = Co for 2)species are held together via hydrogen bonds by coordinated water molecules, lattice water molecules and nitrogen atoms of cyanide groups to form a three-dimensional framework.     

K3[Fe3.26V0.74(OH)O(PO4)4(H2O)2]·2H2O: a synthetic leucophosphite

A new iron(III)/vanadium(III) phosphate, K₃[Fe_3.26V_0.74(OH)O(PO₄)₄(H₂O)₂]·2H₂O (1), has been obtained by hydrothermal synthesis and characterized by single crystal X-ray diffraction, Scanning electron microscopy–energy dispersive X-ray spectroscopy, Inductively coupled plasma atomic emission spectroscopy (ICP), thermogravimetric analysis, and FTIR spectroscopy. Single crystal X-ray diffraction reveals a 3D open framework (monoclinic, space group P2₁/n, a?=?9.6391(7)?Å, b?=?9.8063(7)?Å, c?=?9.7268(7)?Å, β?=?100.71(1)°, and V?=?903.38(11)?ų). This structure presents Fe^III and V^III in a 4.4?:?1?M ratio with the metal ions in two different crystallographic sites. Both metallic centers have distorted octahedral environments, linked by PO₄ tetrahedra, forming channels along the a-axis. The asymmetric unit of K₃[Fe_3.26V_0.74(OH)O(PO₄)₄(H₂O)₂]·2H₂O presents a {M₄(OH)O(PO₄)₄(H₂O)₂}^3? anionic entity, charge balanced by three K⁺, which are located within the channels. It is also possible to distinguish M₄O₂ units whose M^III polyhedra are linked by vertex and edges.     

Synthesis,Crystal Structure and Magnetochemistry of a Novel Trinuclear Iron Complex [Fe 3 O(ClC 6 H 4 CO 2 ) 6 (H 2 O) 2.5 (C 2 H 5 OH) 0.5 ]ClO 4 ·0.5H 2 O

A novel trinuclear iron complex was synthesized in ethanol solution, [Fe 3 O(ClC 6 H 4 CO 2 ) 6 (H 2 O) 2.5 (C 2 H 5 OH) 0.5 ]ClO 4 ·0.5H 2 O. The title complex crystallizes in the tetragonal system, space group $P_{4_1}$     

Tetranuclear bismuth complexes Bi4(O)2(O2CC6H2F3-3,4,5)8 · 2C6H6 and Bi4(O)2(O2CC6H2F3-3,4,5)8 · 2C6H4Me2-1,4: Synthesis and structures

X-ray diffraction study of tetranuclear organobismuth complexes Bi₄(O)₂(O₂CC₆H₂F₃-3,4,5)₈ · 2⁶-C₆H₆ and Bi₄(O)₂(O₂CC₆H₂F₃-3,4,5)₈ · 2(C₆H₄Me₂-1,4) revealed four Bi atoms connected through the bridging carboxylate ligands and the O atoms. The coordination sphere of the terminal Bi atoms includes the chelate carboxylate ligand and the 6-arene molecule. The bridging O atoms are tricoordinated, the distances between the terminal Bi atom and the center of benzene molecule (1,4-dimethylbenzene) are 3.024 Å(3.131 Å).Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 1, 2005, pp. 4–11.Original Russian Text Copyright © 2005 by Sharutin, Egorova, Sharutina, Ivanenko, Adonin, Starichenko, Pushilin, Gerasimenko.     

Synthesis and Structure of Trinuclear Iron Acetate [Fe3O(CH3COO)6(H2O)3][AuCl4]·6H2O

Iron acetate of composition [Fe₃O(CH₃COO)₆(H₂O)₃][AuCl₄]·6H₂O (I) was synthesized and investigated by X-ray diffraction analysis and Mössbauer spectroscopy. The [Fe₃O(CH₃COO)₆(H₂O)₃]⁺ complex cation has a structure typical for ₃-O bridged trinuclear ferric compounds with iron atoms lying at the vertices of a regular triangle with an oxygen atom at the center. The iron atoms are each coordinated by 4 oxygen atoms of the four bridging carboxylic groups, the ₃-O bridging atom, and the coordinated water molecule in the trans-position to the latter. In the trinuclear cation, the Fe(III) ions are coupled by antiferromagnetic exchange interactions with the exchange parameter J = -29.0 cm ^–1 (HDVV model for D _3h symmetry). The specific role of the solvate water molecules in structure formation is discussed.     

Synthesis and Crystal Structure of (C6N3H18)2Ti4O4(C2O4)7·4H2O

The title compound (C6N3H18)2Ti4O4(C2O4)7(4H2O 1 (C13H22N3O18Ti2, Mr = 604.14) was synthesized by the reaction of Ti(SO4)2, H2C2O4(2H2O and N-(2-ammonioethyl)- piperazinium (AEPP) in aqueous solution. The single-crystal X-ray analysis has revealed that 1 crystallizes in the triclinic system, space group Pī with a = 9.1437(6), b = 11.4991(10), c = 11.6975(8)A, α = 96.2915(18), β = 107.998(3), γ = 104.276(4)°, V = 1110.35(14)A3, Z = 2, Dc = 1.807 g/cm3, F(000) = 618, μ = 0.815 mm－1, the final R = 0.0463 and wR = 0.1264 for 3718 observed reflections with I > 2σ(I). X-ray crystal-structure analysis suggests that compound 1 consists of [Ti4O4(C2O4)7]6－ anion and two protonated N-(2-ammonioethyl)piperazinium cations. The anions are linked into an infinite chain through Ti4O4(C2O4)8 by sharing the oxalates as bridging ligands.     

Synthesis and structure of two molybdovanadates containing coordinatively bound oxalato ligands: (NH4)6[Mo6V2O24(C2O4)2]·6H2O and (NH4)4[H2Mo2V2O12(C2O4)2]·2H2O

The compounds (NH₄)₆[Mo₆V₂O₂₄(C₂O₄)₂]·6H₂O (I) and (NH₄)₄[H₂Mo₂V₂O₁₂(C₂O₄)₂]·2H₂O (II) have been prepared from molybdenum(VI) oxide and ammonium vanadate in aqueous solution through the addition of ammonium oxalate, and their structures determined by X-ray structure analysis. Whereas the molybdovanadate anion [Mo₆V₂O₂₄(C₂O₄)₂]⁶⁻ found in (I) consists of six MoO₆ and two VO₆ edge-sharing octahedra of the γ-[Mo₈O₂₆]⁴⁻ type structure, the tetranuclear anion [H₂Mo₂V₂O₁₂(C₂O₄)₂]⁴⁻ of (II) adopts the structure with a M₄O₁₆ core. Both complexes contain bidentate oxalato ligands bonded to the vanadium ions. In both crystal structures the molybdovanadate anions are mutually hydrogen bonded by ammonium ions and water molecules.     

Bis[tetraruthenium(IV)]-containing polyoxometalates: [{Ru(IV)4O6(H2O)9}2Sb2W20O68(OH)2]4- and [{Ru(IV)4O6(H2O)9}2{Fe(H2O)2}2{β-TeW9O33}2H]-

The reaction of [Sb(2)W(22)O(74)(OH)(2)](12-) and [Fe(4)(H(2)O)(10)(β-TeW(9)O(33))(2)](4-) with (NH(4))(2)[RuCl(6)] in aqueous solution resulted in the novel ruthenium(IV)-containing polyanions [{Ru(IV)(4)O(6)(H(2)O)(9)}(2)Sb(2)W(20)O(68)(OH)(2)](4-) and [{Ru(IV)(4)O(6)(H(2)O)(9)}(2){Fe(H(2)O)(2)}(2){β-TeW(9)O(33)}(2)H](-), exhibiting two cationic, adamantane-like, tetraruthenium(IV) units {Ru(4)O(6)(H(2)O)(9)}(4+) bound to the respective polyanion in an external, highly accessible fashion.     

Syntheses and crystal structures of two Cd(II) coordination polymers: one-dimensional chain [Cd(C4H6N2)2(C4H2O4)(H2O)2] n and two-dimensional sheet [Cd(C4H6N2)(H2O)(C4H4O4)] n · n H2O

Two new Cd(II) coordination polymers, [Cd(C₄H₆N₂)₂(C₄H₂O₄)(H₂O)₂] _n (1) (where C₄H₆N₂?=?2-methylimidazole, C₄H₂O₄?=?fumarate), and [Cd(C₄H₆N₂)(H₂O)(C₄H₄O₄)] _n ?·?nH₂O (2), (where C₄H₄O₄?=?succinates), have been prepared and structurally characterized by single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic space group P 1 in a one-dimensional chain structure, in which carboxy is monodentate; a three-dimensional supermolecular network structure was formed through hydrogen bonding. In complex 2, the coordination geometry of the Cd atoms is a pentagonal bipyramid, and a two-dimensional sheet is formed though carboxyl group bridging. In 1 and 2, IR spectra indicate the presence of bridging carboxyl groups, confirmed by structure analyses.     

Synthesis,Structure and Characterization of Three Metal Molybdate Hydrates: Fe(H2O)2(MoO4)2·H3O,NaCo2(MoO4)2(H3O2)and Mn2(MoO4)3·2H3O

Three metal molybdate hydrates,Fe(H2O)2(MoO4)2·H3O(FeMo),NaCo2(MoO4)2(H3O2)(CoMo)and Mn2(MoO4)3·2H3O(MnMo),were synthesized by the mixed-solvent-thermal methods and characterized by singlecrystal X-ray...     

Synthesis and Crystal Structure of a Cyano-bridged Bimetallic Complex [La(betaine)2(H2O)6Fe(CN)6]·2H2O

The title complex [La(betaine)2(H2O)6Fe(CN)6](2H2O (betaine = (CH3)3NCH2CO2) has been synthesized and characterized by X-ray single-crystal structure analysis. The crystal crystallizes in monoclinic, space group P21/n with a = 15.793(5), b = 8.927(3), c = 22.257(7) (A), β = 110.147(5)°, C16H38FeLaN8O12, Mr = 729.31, Z = 4, V = 2946.0(15) (A)3, Dc = 1.640 g/m3, μ(MoKα) = 1.988 mm-1, F(000) =1476, R = 0.0388 and wR = 0.0827 for 4237 observed reflections (I > 2σ(I)). The La3+ ion is nine-coordinated by one cyano nitrogen atom and eight oxygen atoms of two betaine and six water molecules. Each complex molecule is connected to form a 3D network structure by some O-H…O and O-H…N hydrogen bonds.     

配位聚合物{[Co(H2O)6][Co(H2O)4(pmts)]·4H2O}n的合成及晶体结构

以均苯四甲酸(pmts)和CoCl2·6H2O为原料,在碱件水溶液中通过水热法合成了配位聚合物{[Co(H2O)6][Co(H2O)4(pmts)]·4H2O}n,并对其进行了红外、紫外-可见吸收光谱和单品X-射线衍射结构测定.结果表明,Co2+分别与桥配体pmts的1,4位羧基氧及端配体水分子中的氧以轻度畸变的八血体...     

Magnetic relaxation in basic iron(III) carboxylate [Fe3O(O2CPh)6(H2O)3]ClO4·py

The magnetic properties of the antiferromagnetic basic iron(III) carboxylate [Fe(3)O(O(2)CPh)(6)(H(2)O)(3)]ClO(4)·py are studied by magnetic susceptometry and electron paramagnetic resonance spectrocopy. Ac susceptometry under moderate external magnetic fields reveals magnetic relaxation at liquid helium temperatures.     

Syntheses and structures of p-HOOCC6F4COOH · H2O (H2L · H2O) and luminescent coordination polymers [Tb2(H2O)4(L)3 · 2H2O] n and Tb2(Phen)2(L)3 · 2H2O

Compounds p-HOOCC₆F₄COOH · H₂O (H₂L · H₂O), [Tb₂(H₂O)₄(L)₃ · 2H₂O] _n (I), and Tb₂(Phen)₂(L)₃ · 2H₂O (II) are synthesized. According to the X-ray structure analysis data, the crystal structure of H₂L · H₂O is built of centrosymmetric molecules H₂L and molecules of water of crystallization. The crystal structure of compound I is built of layers of coordination 2D polymer [Tb₂(H₂O)₄(L)₃] _n and molecules of water of crystallization. The ligands are the L^2? anions performing both the tetradentate bridging and pentadentate bridging-chelating functions. The coordination polyhedron TbO₉ is a distorted three-capped trigonal prism. Acid H₂L manifests photoluminescence in the UV region (??_max = 368 nm). Compounds I and II have the green luminescence characteristic of the Tb³⁺ ions, and the band with ??_max = 545 nm (transition ⁵ D ₄?? ⁷ F ₅) is maximum in intensity. The photoluminescence intensity of compound II is higher than that for compound I.     

Crystal structure and Raman spectra of [Fe(H2O)6]3+(ClO 4 ? )3·3H2O

Single crystal X-ray diffraction is used to study the structure of colorless crystals isolated from the saturated aqueous solution of trivalent iron perchlorate (TIP) in 67.5% perchloric acid. It is found that the compound crystallizes in the trigonal crystal symmetry; parameters of the hexagonal unit cell: a = b = 16.079(2) ?, c = 11.369(2) ?, ?? = ?? = 90°, ?? = 120°, space group R{ie907-1}(S ₆), Z = 6, ??_calc = 2.021 g/cm³. The structural form of the crystal hydrate is [Fe(H₂O)₆]³⁺(ClO ₄ ^? )₃·3H₂O. The structure contains two independent complex iron cations. Each of them is in the special position {ie907-2}, but retains the regular octahedral structure: average bond lengths are r(Fe-O) = 1.997(1) ?, {ie907-3}O-Fe-O bond angles differ from 90° by only 0.93°. Independent [Fe(H₂O)₆]³⁺ cations form short H-bonds (O??O 2.64 ?) with three crystallization water molecules and somewhat longer H-bonds (O??O 2.73 ?) with three ClO ₄ ^? anions. The ClO ₄ ^? anion is disordered over two positions with occupancies of 0.62(2) and 0.37(2). Both positions correspond to the general position. The outer-sphere crystallization water molecule is characterized by the tetrahedral direction of H-bonds, which it forms with two anions and two independent [Fe(H₂O)₆]³⁺ cations. All water molecules are in the general position. The Raman spectroscopic study of polycrystalline samples reveals weak bands belonging to the internal vibrations of two types of water molecules. The least broad bands are assigned to the transitions of crystallization water molecules whose symmetry is insignificantly lowered by two anion-molecular Hbonds. Anomalously broad bands are assigned to the transitions of a coordinated water molecule whose symmetry is more lowered by intermolecular and anion-molecular H-bonds.     

On the thermal decomposition of [Fe2NiO(CH3COO)6(H2O)3]·2H2O

The heteronuclear-oxoacetate with the composition [Fe₂NiO(CH₂COO)₆(H₂O)₃]·2H₂O decomposed on heating, forming nickel ferrite NiFe₂O₄ and (depending on the decomposition conditions) in part other solid phases. H₂O, CH₃COOH, acetone and CO₂ were also formed in the decomposition. A reaction scheme is given for the decomposition. The products were porous powders with grain diameters between 3 and 10m. On increase of the temperature of decomposition from 300 to 800 C, the BET surface area and the surface area of the pores decreased, but only a small alteration in grain size was observed. As a result of thermal treatment in the temperature region abone 800C, larger aggregates of grains were formed in sintering processes.

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Zusammenfassung Heteronukleare-Oxoazetate der Zusammensetzung [Fe₂NiO(CH₃COO)₆(H₂O)₃]·2H₂O werden durch Erhitzen zersetzt, wobei Nickelferrite NiFe₂O₄ und — in AbhÄngigkeit von den Bedingungen der Zersetzung — mit einem Teil anderer fester Phasen gebildet wird. In der Zersetzungsreaktion werden auch H₂O, CH₃COOH, Azeton und CO₂ gebildet. Es wird ein Reaktionsschema für die Zersetzung angegeben. Die Produkte sind poröse Pulver mit einem Korndurchmesser zwischen 3 und 10 m. Wird die Zersetzungstemperatur von 300 auf 800C erhöht, nimmt die BET-OberflÄche und die PorenoberflÄche ab, wobei sich die Korngrö\e aber nur wenig verÄndert. Im Ergebnis der WÄrmebehandlung im Temperaturbereich oberhalb 800C werden durch Sinterprozesse grö\ere Partikelaggregate gebildet.

     

Synthesis and crystal structure of a novel tartrate copper(II) two-dimensional coordination polymer: {[Cu2(C4H4O6)2(H2O)2]·4H2O}∞

A new 2D coordination polymer, {[Cu₂(C₄H₄O₆)₂(H₂O)₂]·4H₂O}_∞ has been synthesized by the hydrothermal method and characterized by X-ray single crystal diffraction. Every copper(II) atom adopts a distorted octahedral geometry and coordinates with six oxygen atoms from one water molecule and three tartrate acid ions. The two tartrate acid ions have different coordination modes, one provides four oxygen atoms to coordinate with Cu(II) and another coordinates with all six oxygen atoms. Such a coordination mode generates a two-dimensional coordination polymer. In the solid state, the title compound forms a 3D network structure through hydrogen bonds.