Preparation and physicochemical study of sodium hexamolybdometallates(III)

Sodium hexamolybdocobaltate(III) Na₃[CoMo₆O₁₈(OH)₆] · 8H₂O (I) and sodium hexamolybdochromate Na₃[CrMo₆O₁₈(OH)₆] · 8H₂O (II) were synthesized and studied by mass spectrometry, thermogravimetry, powder X-ray diffraction, and IR spectroscopy. The crystals are monoclinic. For compound a = 10.31 Å, b = 10.31 Å, c = 17.55 Å, β = 100.93°, V = 1834.77 ų, ρ_calcd = 3.04 g/cm³, Z = 3; for compound II: a = 10.33 Å, b = 10.33 Å, c = 17.59 Å, β = 100.98°, V = 1835.09 Å3, ρ_calcd = 3.01 g/cm³, Z = 3.     

Tetramminenickel hydrogen hexamolybdometalates(III)

Tetramminenickel hydrogen hexamolybdoaluminate and hexamolybdogallate(III) of compositions [Ni(NH₃)₄] · H[AlMo₆O₁₈(OH)₆] · 10H₂O (I) and [Ni(NH₃)₄] · H[GaMo₆O₁₈(OH)₆] · 10H₂O (II) were synthesized and characterized by mass spectrometry, thermogravimetry, X-ray powder diffraction, and IR spectroscopy. Their crystals are triclinic. For compound I, a= 17.30 Å, b= 14.69 Å, c= 10.45 Å, α = 129.07, β = 65.91°, γ = 138.01°, V = 1338.7l ų, ρ_calcd = 2.75g/cm³, Z = 2; for compound II, a = 17.38 Å, b= 14.75 Å, c= 10.51 Å, α = 131.38°, β= 65.96°, γ = 138.09, V = 1338.15 ų, ρ_calcd = 2.68 g/cm³, Z = 2.     

Synthesis and study of hexaamminecadmium hydrogen hexamolybdocobaltate(III) and hexamolybdochromate(III)

Hexaamminecadmium hydrogen hexamolybdocobaltate(III) and hydrogen hexamolybdochromate(III) of compositions [Cd(NH₃)₆] · H[CoMo₆O₁₈(OH)₆] · 6H₂O (I) and [Cd(NH₃)₆] · H[CrMo₆O₁₈(OH)₆] · 6H₂O (II), respectively, were synthesized and studied by mass spectroscopy, thermo-gravimetry, X-ray powder diffraction, and IR spectroscopy. Crystals of I and II are monoclinic. For I: a = 10.79 Å, b = 3.70 Å, c = 11.95 Å, β = 91.05°, V = 470.12 ų, ρ_calc = 2.37 g/cm³, Z = 2; and for II: a = 10.80 Å, b = 3.68 Å, c = 11.97 Å, β = 91.07°, V = 468.98 ų, ρ_calc = 2.36 g/cm³, Z = 2.     

Synthesis and crystal structures of binuclear complexes of cobalt(II) and cadmium(II) diisobutyldithiophosphinates with hexamethylenetetramine

Heteroligand complexes [Co₂(HMTA)(iso-Bu₂PS₂)₄] (I) (μ_eff = 4.67 μB) and [Cd₂(HMTA)(iso-Bu₂PS₂)₄] (II) have been synthesized. Single crystals of compounds I and II have been obtained. The crystals are monoclinic: a = 32.622(2) Å, b = 9.4891(6) Å, c = 21.7570(13) Å, β = 125.774(1)^o, V = 5464.3(6) Å,³, Z = 4, ρ_calcd = 1.331 g/cm³ for I; a = 34.6092(7) Å, b = 9.5595(2) Å, c = 22.3473(5) Å, β = 127.144(1)^o, V = 5893.5(2) Å, Z = 4, ρ_calcd = 1.355 g/cm³ for II; space group for both complexes C2/c. Structures I and II are based on discrete binuclear molecules. The coordination polyhedra of the Co and Cd atoms are distorted tetragonal pyramids NS₄, with the bases formed by four S atoms of two bidentate chelating ligand iso-Bu₂PS ₂ ^? and the axial vertices occupied by N atoms of bidentate bridging HMTA ligand. The character of interaction of the molecules in structures I and II is considered.     

Synthesis of Cu(II) and Mn(III) Complexes Involving Derivatives of Pyridine

Two complexes with derivatives of pyridine as ligands were synthesized and characterized. From the reaction of 2-pyridinecarboxaldehyde oxime with Cu(OAc)₂ · H₂O afforded the complex C₂₀H₃₀N₆O₁₂Cu₃ (I), and the use of 3-hydroxy-2-pyridinecarboxylic acid with anhydrous MnCl₂ · 4H₂O led to the formation of another complex C₁₂H₁₄N₂OCl₂Mn (II). They were characterized by X-ray diffraction (CIF files CCDC nos. 568718 (I) and 1568880 (II)), NMR, IR and elemental analysis. For I: terigonal, space group R\(\bar 3\)/H, a = 42.548(3), c = 10.2774(9) Å, V = 16113(2) ų, Z = 18, ρ_calcd = 1.367 Mg/m³, the final R factor was R₁ = 0.0945, 6662 for reflections were observed with I > 2σ(I), wR = 0.162 for all data. For II: triclinic, Pī, a = 5.6174(9), b = 7.7259(13), c = 9.7160(16) Å, α = 70.444(3)°, β = 88.009(3)°, γ = 89.818(3)°, V = 397.09(11) ų, Z = 1, ρ_calcd = 1.840 Mg/m³, the final R factor was R₁ = 0.0281, 4280 for reflections were observed with I > 2σ(I), wR = 0.0775 for all data.     

Synthesis and structure of diethylenetriammonium tetrachloroaurates(III)

The (DienH₃)[AuCl₄]₃ · H₂O (I) and (DienH₃)₂[AuCl₄]Cl₅ (II) compounds were obtained by the reaction of HAuCl₄ with diethylenetriamine trihydrochloride (DienH₃Cl₃) in hydrochloric acid. The compounds were characterized by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. Crystals of I and II are monoclinic with space group P2₁/n. For I, a = 12.2314(3) Å, b = 14.6077(5) Å, c = 13.2680(5) Å, β = 106.7350(10)°, V = 2270.22(13) ų, Z = 8. For II, a = 6.62990(10) Å, b = 17.9026(5) Å, c = 10.3661(3) Å, β = 101.9230(10)°, V = 1203.83(5) ų, Z = 2. Both structures are ionic. The gold atoms in I and II have a 4 + 2 coordination environment. The Au-Cl bond lengths are within 2.276–2.294 Å, and the axial Au…Cl contacts are within 3.315–3.405 Å. The diethylenetriammonium cation in I and II has different conformations.     

Three- and four-coordinated silver(I) ions in the coordination polymers [Ag(Me<Subscript>4</Subscript>Pyz)<Subscript>2</Subscript>]PF<Subscript>6</Subscript> and [Ag(2,3-Et<Subscript>2</Subscript>Pyz)<Subscript>2</Subscript>]PF<Subscript>6</Subscript>

The coordination polymers [AgPF₆(Me₄Pyz)₂] (I) and [AgPF₆(2,3-Et₂Pyz)₂] (II) were synthesized, and their structures were determined. Crystals of I are monoclinic, space group C2/c, a = 10.213(2) Å, b = 16.267(3) Å, c = 12.663(3) Å, β = 92.90(3)°, V = 2102.1(7) ų, ρ_calcd = 1.660 g/cm³, Z = 4. The structure of I is built of polymeric zigzag [Ag(C₈H₁₂N₂)] _∞ ⁺ chains and octahedral [PF₆] anions. The coordination polyhedron of the Ag⁺ ion is a flat triangle. Crystals of II are tetragonal, space group P \(\bar 4\)2(1)/c,a = b = 10.641(1) Å, c = 18.942(1) Å, V = 2144.6(2) ų, ρ_calcd = 1.627 g/cm³, Z = 4. In the structure of II, 2D cationic layers of fused square rings exist; the rings consist of four Ag⁺ cations linked by four bridging ligands of diethylpyrazine Et₂Pyz. The coordination polyhedron of the Ag⁺ ion is an irregular four-vertex polyhedron.     

Synthesis and study of sodium vanadomanganate

Sodium 13-vanadomanganate Na₇[MnV₁₃O₃₈]·5H₂O (I) has been synthesized and studied by mass spectrometry, thermogravimetry, IR spectroscopy, and X-ray powder diffraction analysis. The crystals of compound I are monoclinic: a = 11.487 Å, b = 7.613 Å, c = 11.359 Å, β = 114.15°, V = 906.52 ų, ρ_calcd = 2.73 g/cm³, Z = 1.     

Synthesis and physicochemical study of hexaamminechromium(III) hexamolybdogallate

Hexaamminechromium(III) hexamolybdogallate of composition [Cr(NH₃)₆][GaMo₆O₁₈(OH)₆] · 5H₂O (I) was synthesized and studied by mass spectrometry, IR spectroscopy, thermogravimetry, and X-ray diffraction. Crystals I are monoclinic: a = 11.77 Å, b = 10.97 Å, c = 15.49 Å, β = 115.11°, V = 1811.29 ų, ρ_calc = 1.17 g/cm³, Z = 1. The compound obtained was used as a catalyst for soft oxidation of natural gas at 633 K.     

Hexafluorosilicates of cobalt(II) complexes with dimethylsulfoxide and dimethylformamide

New double complexes [Co(DMSO)₆][SiF₆] ? 2H₂O (I) and [Co(DMF)₃(H₂O)₃][SiF₆] ? DMF (II) have been synthesized and studied by IR spectroscopy and X-ray diffraction. Crystals of complex I belong to the tetragonal symmetry system, space group R3?, Z = 3, a = 11.8232(3) Å, c = 18.4699(5) Å, V = 2235.97(10) ų, ρ_calc = 1.573 g/cm³. Crystals of complex II are triclinic, space group P1?, Z = 2, a = 8.6264(4) Å, b = 10.1419(4) Å, c = 13.9657(6) Å, α = 100.847(2)°, β = 98.549(2)°, γ = 93.479(2)°, V = 1181.71(9) ų, ρ_calc = 1.539 g/cm³.     

Synthesis and study of tetraamminecobalt hydrogen hexamolybdochromate

Tetraamminecobalt hydrogen hexamolybdochromate [Co(NH₃)₄] · H[CrMo₆O₁₈(OH)₆] · 6H₂O (I) was synthesized and studied by mass spectrometry, thermogravimetry, IR spectroscopy, and X-ray diffraction. Crystals of I are monoclinic; a = 16.27 Å, b = 5.61 Å, c = 12.36 Å, β = 119.89°, V = 1100.12 ų, ρ_calcd = 2.29 g/cm³, and Z = 1.     

Structure and properties of terbium(III) dipivaloylmethanate and its adducts with Bipy and Phen

The complex of terbium(III) with dipivaloylmethane (2,2,6,6-tetramethylheptane-3,5-dione = Htmhd) [Tb(tmhd)₃]₂ (1) and two its adducts with bipyridyl (Bipy) and phenanthroline (Tb(tmhd)₃·Bipy (2) and Tb(tmhd)₃·Phen (3)) are synthesized and analyzed by single crystal X-ray diffraction. The crystals of [Tb(tmhd)₃]₂ (1) belong to the monoclinic crystal system: P2₁/n space group, a = 12.2238(2) Å, b = 27.6369(5) Å, c = 21.8740(4) Å, β = 105.146(1)°, V = 7133.0(2)ų, Z = 4; the crystals of Tb(tmhd)₃·Bipy (2) and Tb(tmhd)₃·Phen (3) belong to the triclinic crystal system with unit cell parameters: (2) \(P\bar 1\) space group, a = 11.0554(6) Å, b = 12.2761(7) Å, c = 17.7096(8) Å, α = 77.457(2)°, β = 85.557(2)°, γ = 69.659(2)°, V = 2199.8(2) ų, Z = 2; (3) \(P\bar 1\) space group, a = 10.8814(3) Å, b = 12.2852(4) Å, c = 18.3590(6) Å, α = 80.463(1)°, β = 87.587(1)°, γ = 68.640(1)°, V = 2253.6(1) ų, Z = 2. The structures of the complexes are molecular and involve isolated [Tb₂(tmhd)₆] (1), Tb(tmhd)₃·Bipy (2), and Tb(tmhd)₃·Phen (3) molecules. The thermal properties of the obtained terbium complexes are studied by TG-DTA.     

Synthesis and crystal structure of dimethylgold(III) carboxylates

Three novel carboxylate complexes were synthesized: dimethylgold(III) trifluoroacetate [Me₂Au(Tfa)]₂ (I), trimethylacetate (pivalate) [Me₂Au(Piv)]₂ (II), and benzoate [Me₂Au(OBz)]₂ (III). The starting reagent was [Me₂AuI]₂. The procedure of its synthesis provides 60% product yield. Dimethylgold(III) carboxylates were identified from the IR and ¹H NMR data. The title compounds were studied by X-ray diffraction. The unit cell parameters for I, C₈H₁₂Au₂F₆O₄: a = 15.5522(13), b = 12.9398(11), c = 15.6555(14) Å, β = 104.308(2)°, Z = 8, ρ(calcd.) = 2.959 g/cm³, space group C2/c, R = 0.0779; for II, C₁₄H₃₀Au₂O₄: a = 10.3025(3), b = 15.5952(4), c = 12.6819(3) Å, β = 105.8270(10)°, Z = 4, ρ(calcd.) = 2.224 g/cm³, space group P2₁/c, R = 0.0229; for III, C₁₈H₂₂Au₂O₄: a = 12.8050(2), b = 19.7886(3), c = 7.60300(10) Å, Z = 4, ρ(calcd.) = 2.401 g/cm³, space group Pnma, R = 0.0144. Compounds I–III have the molecular structures; the structural units are the [(CH₃)₂Au(OOCR)]₂ dimers (Au…Au 2.984–3.080 Å), R = CF₃, tert-Bu, Ph. The gold atoms have the square coordination with two carbon atoms and two oxygen atoms (Au-O 2.120–2.173 Å). The molecules in compounds I–III are united into infinite unidimensional chains connected by van der Waals interactions.     

Synthesis and study of ammonium hexamolybdobismuthate(III)

Ammonium hexamolybdobismuthate(III) of composition (NH₄)₃[BiMo₆O₁₈(OH)₆] · 7H₂O (I) was synthesized and studied by mass spectrometry, X-ray diffraction, IR spectroscopy, and thermogravimetry. The compound is monoclinic: a = 10.438 Å, b = 7.909 Å, c = 18.127 Å, β = 96.59°, V = 1486.76 ų, ρ_calc = 3.32 g/cm³, Z = 2.     

Synthesis and crystal structures of cobalt(III) and zinc(II) complexes derived from 4-chloro-2-[(2-morpholin-4-ylethylimino)methyl]phenol with urease inhibitory activity

A new mononuclear cobalt(III) complex, [CoL₂(N₃)]₂ · CH₃OH (I), and a new mononuclear zinc(II) complex, [ZnLCl(CH₃OH)] (II) (HL = 4-chloro-2-[(2-morpholin-4-ylethylimino)methyl]phenol), were prepared and structurally characterized by elemental analyses, infrared spectroscopy, and single- crystal X-ray diffraction. The crystal of I is monoclinic: space group P2₁/c, a = 18.742(2) Å, b = 15.197(2) Å, c = 25.646(2) Å, β = 125.996(3)°, V = 5909.8(11) ų, Z = 4. The crystal of II is monoclinic: space group P2₁/c, a = 7.257(1) Å, b = 24.707(2) Å, c = 9.637(1) Å, β = 101.557(2)°, V = 1692.9(3) ų, Z = 4. The Co atom in I is in an octahedral coordination, and the Zn atom in II is in a trigonal-bipyramidal coordination. The urease inhibitory test shows that complex I has strong urease inhibitory activity, while complex II has no activity.     

X-ray study of rhodium(III) sulfates

Compounds with compositions [Rh(H₂O)₆]₂(SO₄)₃·4H₂O (I), (H₃O)[Rh(H₂O)₆](SO₄)₂ (II), [Rh(H₂O)₅OH](SO₄)·0.5H₂O (III), and [Rh(H₂O)₆]₂(SO₄)·(H₂SO₄) _x ·5H₂O (IV) have been studied. The crystal structures of II, III, and IV were determined. All compounds crystallized in the monoclinic crystal system. Crystal data for II: a = 7.279(2) Å, b = 10.512(7) Å, c = 15.806(3) Å, β = 96.71(3)°, space group P2₁/n, Z = 2, d _calc = 2.334 g/cm³; III: a = 20.433(4) Å, b = 7.820(2) c = 11.215(2) Å, β = 114.14(1)°, space group C2/c, Z = 8, d _calc = 2.559 g/cm³; IV: a = 6.2250(4 Å), b = 27.0270(12) Å, c = 7.2674(5) Å, β = 97.04(3)°, space group P2₁/c, Z = 4, d _calc = 2.143 g/cm³. The compounds were studied by IR spectroscopy and powder X-ray diffraction. All of the isolated crystalline phases are sparingly soluble in ethanol and well soluble in water.     

Synthesis and crystal structure of Fe(III) and Al(III) complexes with 2-diphenylacetyl-1,3-indandione

Iron(III) and aluminum(III) complexes with 2-diphenylacetyl-1,3-indandione (HL) have been synthesized. The structures of the obtained compounds FeL₃(I) and AlL₃(II) were studied. The isostructural crystals are monoclinic, I: Z = 8, space group P2_1/c, a = 16.061(3) Å, b = 16.658(3) Å, c = 22.015(4) Å, β = 111.41(3)°; II: Z = 8, space group P2_1/c, a = 16.115(14) Å, b = 16.476(8) Å, c = 21.949(20) Å, β = 111.04(11)°. The structural units of crystals I and II are neutral molecules in which each ligand is bidentately coordinated to a central metal atom through the oxygen atom of the acyl keto group and an oxygen atom of the indandione fragment to form a six-membered chelate ring. In the crystals, neutral molecules I and II form pseudodimers due to stacking of indandione moieties of two adjacent coordination spheres and additional C-H…O contacts. Each pseudodimer is in contact with six neighboring dimers also through hydrogen bonds C-H…O to form an infinite framework.     

Tetra(hexamethylphosphoric triamide) solvate with ammonium tetrakis(isothiocyanato)diamminechromate(III): Synthesis and crystal structure

Ammonium tetrakis(isothiocyanato)diamminechromate(III) crystalline solvate (NH₄)[Cr(NH₃)₂(NCS)₄] ? 4((CH₃)₂N)₃PO (I) has been synthesized and structurally characterized. Crystals of solvate I are tetragonal, space group P \(\overline{4}\)2₁ c, a = 15.8594(3) Å, c = 11.1675(2) ?, V = 2808.86(9) ?³, Z = 2, ρ_calcd = 1.245 g/cm³, ρ_meas = 1.21 g/cm³. Cations, solvate molecules, and anions form chains in a crystal by means of intermolecular hydrogen bonds.     

Syntheses and crystal structures of [Bi(DMSO)<Subscript>8</Subscript>][Fe(NCS)<Subscript>6</Subscript>] and [Al(DMSO)<Subscript>6</Subscript>][Al(NCS)<Subscript>6</Subscript>]

New complexes of composition [Bi(DMSO)₈][Fe(NCS)₆] (1) and [Al(DMSO)₆][Al(NCS)₆] (2) have been prepared, and an octahedral hexarodanoaluminate anion has been structurally characterized for the first time. Crystals of compound 1 are triclinic, space group \(P\bar 1\), a = 11.2368(4) Å, b = 11.4063(4) Å, c = 21.0711(9) Å, α = 92.9520(10)°, β = 99.9430(10)°, γ = 111.9290(10)°, V = 2447.69(16) ų, Z = 2, ρ_calc = 1.680 g/cm³, R ₁ = 0.0564; crystals of compound 2 are cubic, space group \(Pa\bar 3\), a = 15.8201(4) Å, V = 3959.39(17) ų, Z = 4, ρ_calc = 1.462 g/cm³, R ₁ = 0.0475. The bismuth coordination polyhedron BiO₈ in compound 1 is a distorted square antiprism with broken square faces (Bi-O, 2.368-2.582 Å). In the structure of 2, the cation disordered in a complex manner has an octahedral configuration (Al-O, 1.888(11)-1.912(11) Å).     

Synthesis and study of ammonium hexamolybdooxalatovanadate

Ammonium hexamolybdooxalatovanadate of the composition (NH₄)₃[V(C₂O₄)Mo₆O₁₈(OH)₆] · 3H₂O (I) has been synthesized and studied by mass spectroscopy, IR spectroscopy, thermogravimetry, and X_ray powder diffraction. Crystals of I are monoclinic with the unit cell parameters a = 11.9737 Å, b = 18.6533 Å, c = 11.2178 Å, β = 121.021°, V = 3162. 95 ų, M = 1214.01 g/mol, ρ_calcd = 1.91 g/cm³, and Z = 3.