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...     

Preparation of organozirconium aromatic compounds in mixed aqueous-organic solvents: X-ray structures of [Cp2ZrCl(μ2-O′,O′′C-C6H5)], [(CpZr)3(μ2-O′,O′′C-C6H3Cl2)3(μ3-OH)(μ2-OH)3](Cl2C6H3COO)2, and [(CpZr)3(μ2-O′,O′′C-C6H4Cl)3(μ3-OH)(μ2-OH)3]Cl2·CH2Cl2

A new and facile method is presented for the synthesis of zirconocene carboxylate compounds, in which zirconocene dichloride (Cp₂ZrCl₂) is dissolved in 1 M aqueous HCl solution and the requisite ligand is dissolved in an organic solvent. Five such compounds [Cp₂ZrCl(μ₂-O′,O′′C-C₆H₅)] (1), [Cp₂ZrCl(μ₂-O′,O′′C-C₆H₃Cl₂)] (2), [Cp₂Zr(μ₂-O′,O′′C-C₆H₃(OH)Cl)₂] (3), [Cp₂Zr(μ₂-O′,O′′C-C₆H₃(OH)(NO₂))₂] (4), and [Cp₂Zr(μ₂-O′,O′′C-C₆H(OH)Cl₃)₂] (5) have been obtained by this method. The effect of pH on the stability of Cp₂ZrCl₂ in 1 M HCl solution has been investigated by UV/vis spectrophotometry and ¹H NMR spectrometry. The results showed that the aqueous Cp₂ZrCl₂ solutions became less stable with increasing pH, liberating cyclopentadiene. Accordingly, at higher pH (～7), two trinuclear zirconium monocyclopentadienyl compounds, [(CpZr)₃(μ₂-O′,O′′C-C₆H₃Cl₂)₃(μ₃-OH)(μ₂-OH)₃](Cl₂C₆H₃COO)₂ (6) and [(CpZr)₃(μ₂-O′,O′′C-C₆H₄Cl)₃(μ₃-OH)(μ₂-OH)₃]Cl₂·CH₂Cl₂ (7), were obtained. All compounds 1–7 have been characterized by FT-IR, ¹H NMR spectra and elemental analysis. In all of the compounds, the aromatic acid acts as a bidentate ligand in coordinating to the zirconium; both chelating and bridging modes are observed. X-ray crystallographic studies on 1, 6, and 7 have revealed that the geometries at zirconium are distorted octahedral in 6 and 7, and distorted trigonal-bipyramidal in 1.     

Syntheses, X-ray structural characterizations, and thermal stabilities of two nonclassical trinuclear vanadium(IV) complexes, (V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6(H2O) and (V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6(py), and polymeric complexes of stoichiometry (VO(O2PR2)2)∞, R2 = Ph2 and o-(CH2)2(C6H4)

The preparation and structural characterization of two trinuclear vanadium complexes, (V(3)(μ(3)-O)O(2))(μ(2)-O(2)P(CH(2)C(6)H(5))(2))(6)(H(2)O), 1, and (V(3)(μ(3)-O)O(2))(μ(2)-O(2)P(CH(2)C(6)H(5))(2))(6)(py), 2, are reported. In these nonclassical structures, the planar central core consists of the three vanadium atoms arranged in the form of an acute quasi-isosceles triangle with the central oxygen atom multiply bonded to the vanadium atom at the center of the vertex angle and weakly interacting with the two other vanadium atoms on the base sites, each of which contain one external multiply bonded oxygen atom. Reacting VO(acac)(2)in the presence of diphenylphosphinic acid affords (VO(O(2)PPh(2))(2))(∞), 3, while 2-hydroxyisophosphindoline-2-oxide at room temperature in CH(2)Cl(2) affords ((H(2)O)VO(O(2)Po-(CH(2))(2)C(6)H(4))(2))(∞), 4, and at 120 °C in EtOH yields (VO(O(2)P(o-(CH(2))(2)(C(6)H(4)))(∞), 5 on the basis of elemental analyses. The thermal and chemical stability of the complexes were assessed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) measurements. The bond strengths of the vanadium atoms to the OH(2) ligand in 1 and to the NC(5)H(5) ligand in 2 were assessed at 10.7 and 42.0 kJ/mol respectively. Room temperature magnetic susceptibility measurements reveal magnetic moments for trinuclear 1 and 2 at 3.02(1) and 3.05(1) μ(B/mol), and also close to spin only values (1.73 μ(B)) values for 3, 4, and 5 at 1.77(2), 1.758(7), and 1.77(3) μ(B), respectively. Variable-temperature, solid-state magnetic susceptibility measurements were conducted on complex 2 in the temperature range of 2.0-298 K and at an applied field of 0.5 T. Magnetization measurements at 2 and 4 K confirmed a very weak magnetic interaction between the vanadyl centers.     

Tetranuclear azido-bridged copper(II) complex [Cu4(μ-salpn)2(μ1,1-N3)2(N3)2(H2O)2]: Synthesis,characterization and crystal structure

The reaction of salpnH₂ Schiff-base ligand (salpnH₂ = N,N′-bis(salicylidene)-1,3-propylenediamine) with Cu(NO₃)₂·3H₂O and a large excess of NaN₃ (1:2:8 molar ration), lead to the formation of [Cu₄(μ-salpn)₂(μ_1,1-N₃)₂(N₃)₂(H₂O)₂] (1), which has been successfully obtained and characterized by elemental analyses, IR spectroscopy and single-crystal X-ray diffraction. The strong absorption band at about 2000–2100 cm^?1 and at 1597 cm^?1 regions of the IR spectrum of 1 clearly proves the presence of the both end-on (EO) bridging and terminal azido ions and CN (azomethine) groups, respectively. Single-crystal X-ray analyses revealed that the copper atoms are bridged alternately by end-to-on (EO) azido and phenoxo-salpn ligands in the prepared tetranuclear copper(II) complex [Cu₄(μ-salpn)₂(μ_1,1-N₃)₂(N₃)₂(H₂O)₂] (1).     

Synthesis, crystal structure, and thermal stability of [Mo2O4(μ2-O)(C6H4O2)2(H2O)] · (C8H9N2)2 · 2H2O

From hydrothermal treatment of benzene-1,2-diamine, pyrocatechol, and MoO₃ in acetic acid solution, a new compound, [Mo₂(μ₂-O)₂(C₆H₄O₂)₂(H₂O)] · (C₈H₉N₂)₂ · 2H₂O (I), constructed from pyrocatechol chelated dinuclear molybdenum units and 2-methylbenzimidazole has been synthesized. Single-crystal structure analysis reveals that the compound crystallizes in the monoclinic space group P2₁/c with a = 23.365(2), b = 7.2214(5), c = 19.3021(16) β = 97.929(4), V = 3225.6(5), Z = 4, M = 808.46, ρ_c = 1.665 g/cm³, μ(MoK _α) = 0.84 mm^?1, F(000) = 1608, the final R = 0.0622 and wR = 0.1484 for 7385 independent reflections with R _int = 0.0393. Interestingly, an in situ condensation between acetic acid and benzene-1,2-diamine has occurred, and the unexpected 2-methyl-1-H-benzo[d] imidazoles serve as counterions and N-H donors to form stable hydrogen-bond network in the crystal. Furthermore, intermolecular hydrogen bonds are found among the cations, anions and crystalline water molecules. The double nuclear molybdenum units are connected by O-H...O hydrogen bonds with the crystalline water molecules to form one-dimensional chains, and the chains are further joined together by N-H...O to form a quasi-two dimensional structure.     

Synthesis and Molecular and Crystal Structure of K4.5{[Mo3(μ3-Te)(μ2-Te2)3(CN)6]I}I1.5·3H2O and Cs3{[Mo3(μ3-Te)(μ2-Te2)3(CN)6]I}·2H2O

Crystal structures of two new compounds containing trigonal tellurium-bridged cluster fragments [Mo₃(₃-Te)(₂-Te₂)₃]⁴⁺ were investigated. Crystal data for K_4.5{[Mo₃(₃-Te)(₂-Te₂)₃(CN)₆]I}I_1.5·3H₂O: space group , Z = 4, a = 13.280(1), c = 23.800(3) , V = 3635.0(6) ³, d _calc = 3.432 g/cm³, R ₁ = 0.0335, wR2 = 0.0912 for 1378 I _hkl > 2 _I from 3545 measured I _hkl ; for Cs₃{[Mo₃(₃-Te)(₂-Te₂)₃(CN)₆]I}·2H₂O: space group P2 ₁ /n, Z = 2, a= 9.650(2) , b = 22.297(5), c = 27.446(7) , = 94.10(2)°, V = 5890(2) ³, d _calc = 4.273 g/cm ³, R ₁ = 0.0384, wR ₂ = 0.0744 for 957 I _hkl > 2 _I from 3758 measured I _hkl (Enraf-Nonius CAD-4 diffractometer, MoK , graphite monochromator). In both compounds, ionic pairs {[Mo₃Te₇(CN)₆]I}^3– with Te_ax...I^– distances of 3.358-3.676 are formed. In the potassium salt, the {[Mo₃Te₇(CN)₆]I}^3– anion pairs are linked by the additional Te_eqI^– short contacts of 3.460 into two-dimensional corrugated layers perpendicular to the c axis of the unit cell. The structure of the cesium salt is ionic with interstitial H₂O molecules and double-layer closest packing of anions.     

Hydrothermal synthesis and characterization of LaIII and CuII coordination polymers with 5-nitroisophthalic acid (H2Nip), [La2(μ-Nip)(μ-SO4)2(H2O)5] n and {[Cu3(μ-OH)2(μ-Nip)2(μ-H2O)2] · 2H2O} n

3D La^III and 2D Cu^II coordination polymers with 5-nitroisophthalate anions, [La₂(μ-Nip)(μ-SO₄)₂(H₂O)₅] _n (1) and {[Cu₃(μ-OH)₂(μ-Nip)₂(μ-H₂O)₂] ·?2H₂O} _n (2), have been synthesized, characterized and studied by X-ray crystallography. The La atoms have eight–coordinate geometries in distorted square antiprism environments and the Cu atoms have five- and six–coordinate geometries with distorted square pyramidal and octahedral environments. Self-assembly of these compounds in the solid state occurs through coordination and hydrogen bonding.     

Synthesis, Characterization, and Physical Properties of Two Trinuclear, Mixed-Valence Species of Type [μ3-OMnIIMnIII 2(O2CCF3)6(R)3] (R=H2O, CH3COOH)

The preparation and characterization of two new mixed-valence, trinuclear species, [Mn₃O(O₂CCF₃)₆(H₂O)₃]CF₃COOH4/3H₂O (1) and [Mn₃O(O₂CCF₃)₆(CH₃COOH)₃] (2), is reported. Compound 1 crystallizes in the triclinic space group, P¯1 (No. 2), with the parameters, a=12.3131(9) Å, b=12.4427(9) Å, c=12.965(1) Å, =72.593(4)°, =73.453(5)°, =68.345(4)°, V=1727.2(2) ų, and Z=2. A total of 14060 reflections were collected in the range 1.6827.52°. The final weighted and non-weighted agreement indices, R1=0.0589 and wR2=0.1445 were based on a total of 6953 unique reflections with an R _int value of 0.0542. Compound 2 crystallizes in the monoclinic space group, P2₁/n (No. 14), with the parameters, a=12.876(3) Å, b=12.212(4) Å, c=17.732(4) Å, =100.40(3)°, V=3640.4(1) ų, and Z=4. A total of 32197 reflections were collected in the range 1.7227.13°. The final weighted and non-weighted agreement factors, R1=0.0647 and wR2=0.1609 were based on a total of 8018 unique reflections with an R _int value of 0.0462. An investigation of the physical properties revealed that both compounds display an intermediate ground state of S=3/2 as a consequence of intramolecular antiferromagnetic coupling. The magnetic data for compound 1 was best fit to the parameters g=2.09, J=–5.5 cm^–1, J=–3.4 cm^–1, and D _Mn(III)=–4.5 cm^–1; the data for compound 2 was best fit to the parameters g=2.10, J=–2.9 cm^–1, J=–5.5 cm^–1, and D _Mn(III)=–4.5 cm^–1.     

Aquanitrilotris(methylenephosphonato)bis(dimercury(I)) hydrate, [(Hg2)2(H2O)N(CH2PO3)3H2] · H2O: Synthesis,structure, and properties

A reaction of dimercury(I) dinitrate with nitrilotris(methylenephosphonic acid), N(CH₂PO₃)₃H₆, gave the complex [(Hg₂)₂(H₂O){N(CH₂PO₃)₃H₂}] · H₂O. The crystals of the complex are triclinic, space group \(P\bar 1\), Z = 2, a = 8.3436(3), b = 9.0744(3), c = 11.1124(4) Å, α = 91.875(3)°, β = 104.452(3)°, γ = 92.195(3)° (CIF file CCDC no. 1051860). The atoms of either dimercury cation are coordinated differently, making up a distorted tetrahedron and a distorted trigonal bipyramid. The ligand is coordinated to the Hg atoms through seven donor atoms: six (out of nine) O atoms and a N atom. The coordination involves the formation of chelate rings: two four-membered, three five-membered, a six-membered, and an eight-membered ring (CIF file CCDC no. 1051860).     

Synthesis,Structure, and Properties of Cesium Polyuranate [Cs2(H2O)3][(UO2)6O3(OH)8]·2H2O

Russian Journal of General Chemistry - Cesium uranate [Cs2(Н2О)3][(UO2)6O3(OH)8]·2H2O was obtained by reacting hydrated uranium(VI) oxide UO3·2.25H2O with a cesium nitrate...     

Structure of (C3H5NH3)2H2P2O7·H2O

The bis(cyclopropylammonium)dihydrogenodiphosphate monohydrate is a new diphosphate associated with the organic molecule C₃H₅NH₂. We report the chemical preparation and the crystal structure of this organic cation diphosphate. (C₃H₅NH₃)₂H₂P₂O₇.H₂O is orthorhombic (S.G. : P2₁2₁2₁), with Z = 4 and the following unit-cell parameters : a = 4.828(1) Å, b = 11.011(1) Å, c = 25.645(2) Å. The P₂O₇ groups and H₂O water molecules form a succession of bidimensional layers perpendicular to the c axis. The organic cations ensure the three-dimensional cohesion by NH-O hydrogen bonds.     

Synthesis and structure of the organoantimony peroxide solvates [Sb4(μ2-O)4(O2)2(C6H3MeO-2,Br-5)8]·1.5C4H8O2 and [Sb4(μ2-O)4(O2)2(C6H3MeO-2,Br-5)8]·6C4H8O2

The organoantimony peroxide (Ar₂SbO)₄(O₂)₂ (Ar = C₆H₃OMe-2, Br-5) was synthesized by the oxidation of Ar3Sb with hydrogen peroxide in the presence or acetoxime or acetophenone oxime in dioxane. The product crystallizes with various content of the solvent molecules in the crystal unit cell [1.5 (I) and 6 (II), respectively]. An X-ray diffraction analysis of the solvates was performed. Four antimony atoms in the peroxide are in the octahedral coordination, and are linked through bridging oxygen atoms and two peroxide groups. The distances Sb-C, Sb-O_bridge, Sb-O_peroxide, O-O and Sb...Sb are 2.117–2.122, 1.960–1.972, 2.193–2.235, 1.461, 1.465 and 3.223–3.237 Å in I, and 2.112, 2.119, 1.957, 1,966, 2.204, 2,246, 1,467, and 3.2439 Å in II.     

Crystal,molecular, and electronic structure of carboxylate [Fe3O(CH3COO)6(H2O)3]NO3·4H2O

Results of X-ray structural analysis, IR spectroscopy, and quantum chemical study of the [Fe₃O(CH₃COO)₆(H₂O)₃]NO₃·4H₂O complex are reported. The crystal belongs to the monoclinic system with a=15.688(3), b=11.767(2), c=15.318(4) Å, γ=92.54(3)^o, space group P2₁/a, R=0.078. The molecule has a trinuclear structure: three iron atoms occupy the vertices of an equilateral, triangle with an Fe−Fe distance of 3.29 Å and are bonded by the μ₃-oxo and μ-CH₃COO⁻ (O,O′) ligands. To each iron atom, one water molecule is coordinated. Using the obtained values of populations on 3d AO of Fe (d _xy ^1.34 ; d _xz ^1.39 ; d _yz ^1.46 ; ; ) and charges on oxygen atoms (O _c ^−0.5 ; O _ac ^−0.31 ; O _w ^−0.31 ), we estimated the values of isomeric shift and quadrupole splitting (0.75 and 0.70 mm/sec, respectively; these are close to the experimental values of 0.75 and 0.58 mm/sec, (300 K)). Institute of Chemistry, Moldovian Academy of Sciences. Moldovian State University. Institute of Applied Physics, Moldovian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii., Vol. 35, No. 2, pp. 112–120, March–April, 1994. Translated by T. Yudanova     

Syntheses and Crystal Structures of Two Trinuclear Iron(Ⅲ) Carboxylate Complexes: [Fe3(μ3-O)(μ-O2CEt)6(H2O)3]Cl.3H2O and [Fe3(μ3-O)(μ-O2CEt)6Py3]Cl(Py=pyridine)

Two new oxo-centered trinuclear iron complexes [Fe3(μ3-O)(μ-O2CEt)6(H2O)3]Cl.3H2O 1 and [Fe3(μ3-O)(μ-O2CEt)6Py3]Cl 2 were prepared in non-aqueous solvent and their crystal structures have been determined. Crystal 1 is monoclinic, space group P21/n, a=9.909(3), b=24.467(8), c=14.542(7)(), β=107.85(4)° V=3356(4)()3, Z=4, Mr=765.52, Dc=1.52 g/cm3, μ=14.28 cm-1, F(000)=1588 and R=0.059, Rw=0.071 for 3745 unique reflections with I>3σ(I). Crystal 2 belongs to the monoclinic system with space group C2/c, a=13.750(3), b=18.439(4), c=16.696(3)(), β=93.42(3)°, V=4226(3)()3, Z=4, Mr=894.73, Dc=1.41 g/cm3, μ=11.4 cm-1, F(000)=2322 and R=0.058, Rw=0.062 for 2272 unique reflections with I>3σ(I). The two structures contain the same trimetal framework in which three iron(Ⅲ) atoms form a nearly equilateral triangle with a μ3-oxygen atom in the centre.     

Bis(μ3-barbiturato−O,O,O′)-(μ2-aqua)- aqua-barium(II): crystal structure,spectroscopic and thermal properties

A polymeric coordination compound, [Ba(H₂O) ₂(Hba)₂] (1) (H₂ba – barbituric acid, C₄H₄N₂O₃), was obtained. The structure of 1 was solved using powder X-ray diffraction methods. The Ba²⁺ ion in 1 formed a three-capped trigonal prism. The BaO₉ polyhedra, connected with each other by the edges and faces, formed a chain. Several 4- and 12-membered cycles due to the bridging μ₂-H₂O and bridging μ₃-Hba^– also formed implementing a 3-D polymer structure. The structures of 1 and other thiobarbiturate complexes were compared. The replacement of a S atom by an O atom in the heterocyclic ligand Htba^? (thiobarbiturate ion) of the compound Ba(H₂O)₂(Htba)₂ resulted in changes of the coordination number Ba(II) and supramolecular structure. The intermolecular hydrogen bonds O–H?O and N–H?O formed a 3-D net where pronounced 2-D layers of Hba^– ions could be found. A new topological net in 1 was observed. The IR and thermal stability were investigated.     

Syntheses and characterization of the vanadium trimer (V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6(4,4′-bipyridine) and the vanadium hexamer [(V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6]2(μ2-N1,N2-di(pyridin-4-yl)oxalamide)

Reacting VO(acac)₂ with six equivalents of dibenzylphosphinic acid in the presence of 4,4′-bipyridine or μ₂-N¹,N²-di(pyridin-4-yl)oxalamide leads to trimeric (V₃(μ₃-O)O₂)(μ₂-O₂P(CH₂C₆H₅)₂)₆(4,4′-bipyridine) or the hexamer [(V₃(μ₃-O)O₂)(μ₂-O₂P(CH₂C₆H₅)₂)₆]₂(μ₂-N¹,N²-di(pyridin-4-yl)oxalamide). The complexes were characterized by spectroscopic (FTIR and ¹H NMR spectroscopies), TGA, and by single crystal X-ray diffraction measurements. The structures consist of a planar central core where three vanadium ions are arranged in the form of a quasi-isosceles triangle and contain an interstitial O which is multiply bonded to one V and weakly interacting at different bond distances to the remaining two V ions.     

Syntheses, Crystal Structures and Characterization of Two Zeotype Crystals of K4[Cr3O(H2O)3(OOCH)6]2[P2W18O62] ·9.5H2O and K4[Cr3O(H2O)3(OOCH)6[H3P2W17Co(H2O)O61]·20H2O

Two novel zeotype crystals, K4[Cr3O(H2O)3(OOCH)6]2[P2W18O62]·9.5H2O(1) and K4 [Cr3O(H2O)3·X-ray single crystal diffraction. Crystal data: C12H43O103.5K4Cr6P2W18(1), hexagonal P6(3)/m, a=1.5895(2)nm, b=1.5895(2) nm, c=2.1620(4) nm, α=90°, β=90°, γ =120°, V=4.7305(13) nm3, Z=2,R1 =0. 0726, wR2=0. 1542; C6H57O98K4Cr3CoP2W17(2), hexagonal P6(3)/mmc, a=1. 61328 (3) nm, b=1.61328(3) nm, c=2. 06613 (9) nm, α=90°,β=90°, γ=120°, V=4. 6570(2) nm3, Z=2, R1=0. 0377,wR2 =0.1070. These crystals were characterized using elemental analysis, IR, TG-DTA, and XRD. It was found that the polyoxometalate anions maintained Wells-Dawson structure for crystal 1 and lacunary Wells-Dawson structure for crystal 2. Thermal analysis showed that crystal 1 lost the water of crystallization at 132 ℃, whereas crystal 2 lost the water of crystallization at 100 ℃. Crystal 1 could reversibly desorb and adsorb water molecules and its crystal structure could be restored after re-adsorbing the water molecules. It was also found from the XRD patterns that the void size of crystal 2 is smaller compared with that of crystal 1, which is attributed to the higher anion charges.     

[Gd(Gly)3(H2O)2]Cl3·H2O的合成与晶体结构

氯化钆;甘氨酸;固态配合物;[Gd(Gly)3(H2O)2]Cl3·H2O的合成与晶体结构     

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.