Organometallic polymers MF<Subscript>3</Subscript>(4,4′-Bipy) with M = Ga and In

Organometallic polymers MF₃(4,4′-Bipy) with M = Ga and In are synthesized by the hydrothermal method. According to X-ray diffraction data, in a metal atom in the polymeric structure is octahedrally coordinated by four fluorine atoms and two nitrogen atoms. Bridging fluorine atoms and bidentate-bridging 4,4′-Bipy molecules join the complexes into layers.     

Two novel sandwich copper(II) complexes [CuLCl]<Subscript>2</Subscript>[CuCL<Subscript>4</Subscript>] and [CuLBr]<Subscript>2</Subscript>[CuBr<Subscript>4</Subscript>] (L = N,N′-bis(furaldehyde)diethylenetriamine)

The novel trinuclear copper(II) complexes [CuLCl]₂[CuCl₄](I) and [CuLBr]₂[CuBr₄] (II) (where L = N,N′-bis(furaldehyde) diethylenetriamine) were synthesized and structurally characterized by X-ray diffraction. They consist of sandwich units. Both I and II crystallize isomorphously in the monoclinic space group P2/n and feature cation/anion/cation geometry. The novel trinuclear copper(II) complexes I and II shown to be stabilized by a number of weak hydrogen bonds and intermolecular π-π stacking interactions. The article is published in the original.     

Geometric and electronic structure of an N,N′-ethylene-bis(salicylaldiminato) zinc(II) molecule,ZnO<Subscript>2</Subscript>N<Subscript>2</Subscript>C<Subscript>16</Subscript>H<Subscript>14</Subscript>

Gas electron diffraction at a temperature T of 641(5) K is used to study the structure of an N,N′-ethylenebis(salicylaldiminato) zinc(II) molecule, ZnO₂N₂C₁₆H₁₄, further Zn(salen). The structure of a gaseous Zn(salen) complex has C ₂ symmetry and is characterized by a substantial turn of two chelating fragments of the ligand with respect to each other, and also by a big difference in the length of coordination bonds: r _h1(Zn-O)=1.902(7) Å r _h1(Zn-N)= 2.027(7) Å. Results of the DFT/B3LYP calculation with 6-31G* and CEP,TZV basis sets of the molecule structure well agree with the experimental data. The electronic structure of Ni(salen), Cu(salen), Zn(salen), and Zn(acacen) molecules is considered.     

Hydrothermal synthesis and crystal structure of a tungstovanadate: [4,4′-bipyH<Subscript>2</Subscript>][4,4′-bipyH]<Subscript>2</Subscript>[VW<Subscript>12</Subscript>O<Subscript>40</Subscript>] · 4,4′-bipy · 7.5H<Subscript>2</Subscript>O

An organic-inorganic hybrid Keggin compound, [4,4′-bipyH₂][4,4′-bipyH]₂[VW₁₂O₄₀] · 4,4′-bipy · 7.5H₂O (bipy-bipyridine) (1), has been prepared under hydrothermal conditions and characterized by IR spectroscopy, single crystal X-ray diffraction, thermal analysis, and ESR spectroscopy. 1 crystallized in the monoclinic space group P2₁/c with a = 18.7350(15) Å, b = 14.0253(12) Å, c = 26.434(2) Å, β= 105.0810(10)°, V = 6706.6(10) ų and Z = 4. The crystal structure of 1 consists of diprotonated and monoprotonated 4,4′-bipyridine cations, free 4,4′-bipyridine molecule, lattice water molecules, and a typical Keggin-type polyoxoanion [VW₁₂O₄₀]^4?. The polyoxoanion is constructed by four {W₃O₁₆} trinuclear groups, each of which is made up of three edge-sharing {WO₆} octahedra, and the {VO₄} tetrahedron is in the center of the cage.     

Fullerides: heterometallic superconductors with composition M<Subscript>2</Subscript>M′C<Subscript>60</Subscript> (M = K,Rb; M′ = Yb,Lu, Sc)

One- or two-step reactions of potassium and rubidium fullerides with composition M_k C₆₀ (M = K, Rb; k = 3—6) and K₆C₆₀ + m K mixtures (m = 1, 3) with anhydrous salts MCl₃ (M = La, Pr, Nd, Sm, Gd, Tb, Yb, Lu, Y, Sc) and YbI₂ in a toluene—THF medium afforded heterometallic fullerides M_3–nM_nC₆₀ (n = 1—3). Among these compounds, substituted fullerides with composition M₂MC₆₀ (M = Yb, Lu, Sc) display superconducting properties with critical temperatures of 14—20 K.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1623–1628, August, 2004.     

Pyrazolate-bridged binuclear zinc complexes Zn<Subscript>2</Subscript>(μ-dmpz)<Subscript>2</Subscript>(Hdmpz)<Subscript>2</Subscript>(OOCR)<Subscript>2</Subscript> (R = Me,Ph; Hdmpz = 3,5-dimethylpyrazole)

Triethylamine reacts with aqueous zinc acetate and the product of its thermolysis in the presence of benzoic acid to yield the complexes [Zn₇(μ₄-O)(μ-OOCMe)₁₀][η-OC(Me)OHNEt₃]₂ (1) and [Zn₂(μOOCPh)₄][η-OC(Me)OHNEt₃]₂ (2), respectively. The reactions of 1 and 2 with 3,5-dimethylpyrazole at room temperature in benzene yield pyrazolate-bridged binuclear complexes Zn₂(μdmpz)₂(Hdmpz)₂(OOCR)₂ (R = Me (3), Ph (4)). The structures of complexes 1–4 have been determined by X-ray crystallography.     

Synthesis and crystal structure of a 1D coordination polymer Cu<Subscript>3</Subscript>(Mip)<Subscript>4</Subscript>(2,2′-Bipy)<Subscript>2</Subscript> (H<Subscript>2</Subscript>Mip = 5-methylisophthalic acid, 2,2′-Bipy = 2,2′-bipyridine)

A new metal-organic coordination polymer Cu₃(Mip)₄(2,2′-Bipy)₂ (I), where H₂Mip = 5-methylisophthalic acid, 2,2′-Bipy = 2,2′-bipyridine has been hydrothermally synthesized and characterized by IR, elemental analysis, single-crystal X-ray diffraction analysis, and powder X-ray diffraction. The X-ray diffraction analysis reveals that I crystallizes in the triclinic crystal system, space group P \(\bar 1\) and exhibits a one-dimensional chain structure, which contains a trinuclear [Cu₃(Mip)₂(HMip)₂(2,2′-Bipy)₂] subunit, and the adjacent subunits are bridged by Mip anions into a 1D chain. Unit cell parameters for I: a = 10.239(2), b = 11.249(2), c = 11.971(2) Å, α = 82.01(1)°, β = 65.03(2)°, γ = 84.32(2)°, V = 1236.5(4) ų, Z = 2.     

Synthesis and study of lead(II) uranate Pb(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>O<Subscript>2</Subscript>(OH)<Subscript>2</Subscript>·H<Subscript>2</Subscript>O

An individual crystalline compound Pb(UO₂)₂O₂(OH)₂·(H₂O) was obtained by reaction of synthetic schoepite UO₃·2.25H₂O with an aqueous solution of lead(II) nitrate under hydrothermal conditions. The composition and structure of this compound were determined, and the processes of its dehydration and thermal decomposition were studied by chemical analysis, X-ray diffraction, IR spectroscopy, and thermography.     

Crystal structure and vibrational spectra of M[VO<Subscript>2</Subscript>(SeO<Subscript>4</Subscript>)(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>]·H<Subscript>2</Subscript>O (M = K,Rb, NH<Subscript>4</Subscript>)

By the hydration of MVO(SeO₄)₂ with saturated water vapors at room temperature a series of isostructural complex compounds of vanadium(V) of the composition M[VO₂(SeO₄)(H₂O)₂]·H₂O (K, Rb, NH₄) are synthesized and their physicochemical properties are studied. Based on the X-ray and neutron diffraction data, it is found that their crystal structure is composed of VO₆ octahedra linked in infinite chains by bridging SeO₄ tetrahedra. Each of the VO₆ octahedra has two short terminal V-O bonds forming a bent dioxovanadium group VO₂⁺. Two water molecules are coordinated by vanadium and one molecule is out of the first coordination sphere in the interchain space. The vibrational spectra of the studied compounds are completely consistent with their structural features.     

Nickel(II) and Iron(II) coordination compounds with octahydrotriborate(1–) anion [ML<Subscript>3</Subscript>]{B<Subscript>3</Subscript>H<Subscript>8</Subscript>}<Subscript>2</Subscript> (M = Fe<Superscript>2+</Superscript>, Ni<Superscript>2+</Superscript>; L = bipy,phen)

Methods of synthesis have been developed for new types of promising precursors of metal borides, coordination compounds [ML₃]B{₃H₈{₂ (M = Fe²⁺, Ni²⁺; L = bipy, phen), using modified procedures of synthesis of octahydrotriborate anion. Compounds [Ni(bipy)₃]B{₃H₈}₂, [Ni (phen)₃]B{₃H₈}₂ and [Fe(phen)₃]B{₃H₈}₂ were prepared and characterized by single-crystal X-ray diffraction.     

Crystal structures of chiral (R/S) (C<Subscript>8</Subscript>H<Subscript>11</Subscript>N)<Subscript>2</Subscript> · Zn(OAc)<Subscript>2</Subscript>

Two opposite configuration (R/S) of chiral complexes (C₈H₁₁N)₂ · Zn(OAc)₂ (Ia and Ib—L-(−)-) and D-(+)-isomer) were synthesized by a simple one-pot method. The crystal structures of Ia and ib determined by X-ray crystallography.     

Synthesis and structure of trinuclear pyrazolate-bridged acetates M<Subscript>3</Subscript>(μ-dmpz)<Subscript>4</Subscript>(Hdmpz)<Subscript>2</Subscript>(OOCMe)<Subscript>2</Subscript> (M = Zn or Co; Hdmpz = 3,5-dimethylpyrazole)

We discovered that reactions of hydrous cobalt and zinc acetates with 3,5-dimethylpyrazole (Hdmpz) in boiling xylene or toluene or upon the thermolysis of solid precursors (150°C) yield trinuclear pyrazolate-bridged complexes M₃ (μ-dmpz)₄(Hdmpz)₂ (OOCMe)₂(M = Zn or Co). Depending on the crystallization conditions, these complexes contain various solvating molecules (benzene, toluene, or Hdmpz), which influences the character of intramolecular and intermolecular hydrogen bonding, as shown by X-ray crystallography.     

Synthesis and luminescent properties of the complexes EuL(<Emphasis Type="Italic">i</Emphasis>-Bu<Subscript>2</Subscript>PS<Subscript>2</Subscript>)<Subscript>2</Subscript>(NO<Subscript>3</Subscript>) (L = Phen, 2,2′-Bipy, 4,4′-Bipy)

The mixed ligand coordination compounds EuL(i-Bu₂PS₂)₂(NO₃) (L = Phen, 2,2′-Bipy, 4,4′-Bipy) are synthesized. On the basis of X-ray analysis and IR spectra their structures are elucidated. The complexes containing Phen or 2,2′-Bipy are found to possess photoluminescent property.     

[H<Subscript>4</Subscript>(4,4′-Bipy)<Subscript>3</Subscript>][Sc(OH)(H<Subscript>2</Subscript>O)<Subscript>5</Subscript>]<Subscript>2</Subscript>Cl<Subscript>8</Subscript>: Synthesis,structure, and solid-phase thermal transformation

The reaction of [Sc(OH)(H₂O)₅]₂Cl₄ · 2H₂O in isopropanol with 4,4′-Bipy in CHCl₃ produced a crystalline compound, which was identified as [H₄(4,4′-Bipy)₃][Sc(OH)(H₂O)₅]₂Cl₈ (I) by elemental analysis, IR spectra, and single-crystal X-ray diffraction. In the structure of compound I, the three protonated diimine molecules form a centrosymmetric trimer via N...N hydrogen bonds. The polyhedron around the Sc atom is an octahedron with one split vertex. The excursion of the Sc atom from the plane formed by the oxygen atoms (water molecules) toward the hydroxo bridges is 0.5 Å. The thermolysis of compound I generates ScCl₃, whereas the final decomposition product of the precursor dimer is ScOCl.     

Synthesis,characterization, spectroscopic,and thermal studies of imidazole complexes of metal benzenesulfonates. Crystal structure of [M(imH)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>]·(BS)<Subscript>2</Subscript> [M=Ni(II) and Co(II)]

Four novel transition metal benzenesulfonate (BS) complexes of imidazole (im) with a general formula [M(imH)₃(H₂O)₃]·(BS)₂ [M=Mn(II) (1), Ni(II) (2), Co(II) (3)] and [Cu(BS)(imH)₃]·(BS) (4) have been synthesized and characterized by physicochemical and spectroscopic methods. The complexes 2 and 3 have also been characterized by single X-ray diffraction technique. The BS anion in complexes 1–3 acts as a counter anion, while in complex 4, it acts as both ligand and counter anion. The Ni and Co complexes are isomorphous, crystallizing in the monoclinic crystal system with C2/c space group. Each metal(II) atom in 2 and 3 is octahedrally coordinated by three imidazole and three aqua ligands, adopting a mer-coordination mode with Ni(II) or Co(II) centers. In both 2 and 3, the H2C atom has bifurcated donor (O3 and O5) atoms, forming a bifurcated hydrogen bond. This hydrogen bond links the complex cation and BS anion, forming one-dimensional hydrogen-bonded supramolecular chains. The complexes exhibit different decomposition characteristics. Magnetic susceptibility measurement shows that complex 3 has orbital interactions.     

Hydrothermal synthesis and crystal structure of a novel nickel(II) complex: [Ni(H<Subscript>2</Subscript>Bibzim)<Subscript>3</Subscript>Cl<Subscript>2</Subscript> · 2H<Subscript>2</Subscript>O] (H<Subscript>2</Subscript>Bibzim = 2,2-Bibenzimidazole)

A novel organic-inorganic hybrid compound based on weak intermolecular interactions formulated as Ni(H₂Bibzim)₃Cl₂ · 2H₂O (H₂Bibzim = 2,2-bibenzimidazole, formula, C₁₄H₁₀N₄) has been synthesized under hydrothermal conditions and characterized by elemental analysis, single-crystal X-ray diffraction analyses, and IR spectra. It crystallizes in the orthorhombic system, space group Pbcn, Z = 2, a = 20.8530(19), b = 15.7838(14), c = 12.3159(11) Å, V = 4053.7(6) ų, M _r = 1736.84, ρ_c = 1.423g/cm³, λ = 0.71073 Å, μ(MoK _α) = 0.664 mm^?1, F(000) = 1792, R = 0.0283 and wR = 0.0707 for 3746 observed reflections with I > 2σ(I). The complex is composed of mononuclear cations [Ni(H₂Bibzim)₃]²⁺, chlorine anions, and lattice water molecules, which are linked into a two-dimensional supramolecular architectures via hydrogen bonds and π-π-stacking interactions.     

Synthesis,properties, and catecholase-like activity of the [1,4-di(6′-methyl-2′-pyridyl)aminophthalazine]dimanganese(II) complex,Mn<Subscript>2</Subscript>(6′Me<Subscript>2</Subscript>PAP)<Subscript>2</Subscript>Cl<Subscript>4</Subscript>

The preparation, spectroscopic properties, and catecholase-like activity of the dimanganese(II) complex [Mn₂(6′Me₂PAP)₂Cl₄] [6′Me₂PAP: 1,4-di(6′-methyl-2′-pyridyl)aminophthalazine] are reported. The title compound was suitable catalyst for the oxidation of 3,5-di-t-butylcatechol (3,5-DTBCH₂) to 3,5-di-t-butyl-1,2-benzoquinone (3,5-DTBQ) with dioxygen under ambient conditions in good yields. The catalytic oxidation was found to obey Michaelis–Menten type kinetics.     

Synthesis and structure of M[UO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)(NCS)] · 0.5H<Subscript>2</Subscript>O (M = Rb or Cs)

Single crystals of M[UO₂(C₂O₄)(NCS)] · 0.5H₂O (M = Rb (I) or Cs (II)) have been synthesized and studied by X-ray diffraction analysis. The compounds are isostructural, and their crystals are monoclinic with the space group C2/c, Z = 4, and unit cell parameters: a = 9.0624(5) Å, b = 13.1242(7) Å, c = 8.9204(5) Å, β = 98.897(2)°, R = 0.0226 (I); a = 9.3171(3) Å, b = 13.2987(5) Å, c = 9.1151(3) Å, β = 101.0860(10)°, R = 0.0214 (II). The main structural units of the crystals of I and II are the [[UO₂(C₂O₄)(NCS)]^? chains belonging to the crystal-chemical group AK⁰²M¹ (A = UO ₂ ²⁺ , K⁰² = C₂O ₄ ^2? , M¹ = NCS^? of the uranyl complexes. The uranium-containing chains are joined into a three-dimensional framework through electrostatic interactions with the outer-sphere cations and hydrogen bonds involving the water molecules.     

Crystal structure and thermal properties of [Au(en)<Subscript>2</Subscript>]<Subscript>2</Subscript>[Cu(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>]<Subscript>3</Subscript>·8H<Subscript>2</Subscript>O

The crystal structure of a double complex salt of the composition [Au(en)₂]₂[Cu(C₂O₄)₂]₃·8H₂O (en = ethylenediamine) at 150 K is determined by single crystal X-ray diffraction. The crystal data for C₂₀H₄₈Au₂Cu₃N₈O₃₂ are: a = 9.1761(3) Å, b = 16.9749(6) Å, c = 13.4475(5) Å, β = 104.333(1)°, V = 2029.43(12) ų, P2₁/c space group, Z = 2, d _x = 2.450 g/cm³. It is demonstrated that the thermal decomposition of the double complex salt in a helium or hydrogen atmosphere affords the solid solution Au_0.4Cu_0.6.     

Reactions of 2,2′-Pyridyl with the cadmium(II) compounds: Synthesis,crystal structure,and luminescence properties of [Cd(Pic)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>] · H<Subscript>2</Subscript>O

The reactions of 2,2'-pyridyl, (2-Py)C(O)C(O)(2-Py), with the Cd(II) compounds under various conditions are studied. The medium and nature of the anions exert a decisive effect on the compositions and structures of the formed cadmium complexes. The reaction of cadmium diacetate with 2,2'-pyridyl in an aqueous-alcohol medium in air affords coordination compound [Cd(Рic)₂(H₂O)₂] · H₂O (I) (Pic^? is picolinate ion, CO₂C₅H₄N), and its crystal structure is determined. The crystals are monoclinic: space group P2₁/c, a = 7.499(1), b = 15.676(1), с = 12.719(1) Å, β = 94.79(1)°, V = 1490.0(2) Å3, Z = 4, ρ_calcd = 1.502 g/cm³. The molecular packing of compound I is a supramolecular 3D framework consisting of discrete complexes [Cd(Pic)₂(H₂O)₂] linked by hydrogen bonds O–H…O. The coordination sphere of Cd²⁺ contains two O atoms and two N atoms of the ligand and two water molecules. The coordination polyhedron of Cd²⁺ is a distorted octahedron.