Synthesis, crystal structures, and properties of [Ca(H2O)2(Dmf@CB[6])(Bdc)] · DMF · 4H2O and [Ca(H2O)3(Dmf@CB[6])]Cl2 · 2H2O

Complexes [Ca(H₂O)₂(Dmf@CB[6])(Bdc)] · DMF · 4H₂O (I) and [Ca(H₂O)₃(Dmf@CB[6])]Cl₂ · 2H₂O (II) are synthesized by the heating (95°C) of a mixture of calcium chloride and cucurbit[6]uril (CB[6]) in a mixture of dimethylformamide (DMF) and water with the addition of terephthalic acid (H₂Bdc) in the case of complex I or triethylamine for complex II. The compounds are characterized by X-ray diffraction analysis, IR spectroscopy, and thermogravimetric and elemental analyses. The luminescence spectra are also recorded. According to the X-ray diffraction data, the calcium atom is coordinated by the oxygen atoms of the cucurbit[6]uril molecule, water molecules, and terephthalate anion (for I). The internal cavity of the cavitand is occupied by DMF.     

Synthesis, crystal structure, and thermal analysis of hexahydrogen dodecavanadate of composition [NH3 · H2O]6 · H6[Ca4V12O40] · 6H2O

Dihydrogen dodecavanadate of composition [NH₃ · H₂O]₆ · H₆[Ca₄V₁₂O₄₀] · 6H₂O was synthe-sized and studied by X-ray crystallography and TGA analyses. The crystals are cubic, space group I $\bar 4$ 3m;; unit cell parameters: a = 13.518(2) ?, V = 2470.4(3) ?³, ??_calc = 2.2334 g/cm³, Z = 2.     

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 (H3O)(C3H5N2)[Mn(OH)6 Mo6O18]·3.5H2O and (H3O)3[Co(OH)6Mo6O18]·7H2O

The crystals of the title compounds (H3O)(C3H5N2)[Mn(OH)6Mo6O18]·3.5H2O 1 and (H3O)3[Co(OH)6Mo6O18]·7H2O 2 have been prepared and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 21.5018(9), b = 10.9331(5), c = 11.8667(5)A,β = 95.3570(10)o, V = 2777.5(2)A3, Z = 4, Dc = 2.802 g/cm3, Mr = 1171.80,μ(MoKα) = 3.173 mm-1, F(000) = 223, the final R = 0.0458 and wR = 0.1041 for 2093 observed reflections (I>2σ(I)); Compound 2 crystallizes in monoclinic, space group P21/c with a = 11.4042(12), b = 10.9481(11), c = 11.6722(12)A, β= 99.948(2)o, V = 1435.4(3)A3, Z = 2, Dc = 2.794 g/cm3, Mr = 1207.80,μ(MoKα) = 3.223 mm-1, F(000) = 1160, the final R = 0.0544 and wR = 0.1066 for 1906 observed reflections (I > 2σ(I)). Both compounds 1 and 2 adopt the Anderson structure, in which the anion is of centrosymmetry and formed by six octahedral edge-sharing MoO6 units surrounding the central MO6 (M = Mn or Co) octahedron.     

Synthesis, properties, and thermal decomposition of compounds [Co(En)3][Fe(CN)6] · 2H2O and [Co(En)3]4[Fe(CN)6]3 · 15H2O

Binary complex salts, [Co(En)₃][Fe(CN)6] · 2H₂O and [Co(En)₃]₄[Fe(CN)₆]₃ · 15H₂O, are synthesized. The properties of the salts and their thermolysis in air, dihydrogen, and argon are studied. Oxides of the central ions of the binary complex salts are found to be the thermolysis products in an oxidative atmosphere. Solid solutions (intermetallic compounds) CoFe are the thermolysis products in the reductive atmosphere, whereas intermetallides containing considerable amounts of C and N and an impurity of Co and Fe oxides are the thermolysis products in an inert atmosphere. Gaseous thermolysis products in dihydrogen and argon are NH₃, hydrocarbons, and ethylenediamine.     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

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...     

Synthesis and Crystal Structure of Two Decavanadates Cluster Metal Complexes: [Co(H2O)6]2[H2V10O28]·6H2O and (NH4)2[Ca(H2O)7]2[V10O28]

Two new decavanadate metal complexes, [Co(H₂O)₆]₂[H₂V₁₀O₂₈]·6H₂O (1) and (NH₄)₂[Ca(H₂O)₇]₂[V₁₀O₂₈] (2), have been synthesized under hydrothermal condition by using chlorhydric acid as the initiator at 120 °C. The aqueous NaVO₃ solution with an aqueous solution of CoCl₂·6H₂O were used for generating 1 and aqueous CaCl₂·2H₂O and NH₄VO₃ solution were employed for creating 2. Compound 1 consisted of discrete hexa-aqua-cobalt [Co(H₂O)₆]²⁺ cations, [H₂V₁₀O₂₈]⁴⁻ anions and non-coordination water molecules. Compound 2 were composed of hepta-aqua-calcium [Ca(H₂O)₇]²⁺ cations, ammonium NH₄ ⁺ and [V₁₀O₂₈]⁶⁻ anion. For compound 2, the distorted pentagonal bipyramid [Ca(H₂O)₇]²⁺ is uncommon. In the crystal lattice, hydrogen bonds played an important role on connecting cations, anions and non-coordinated water molecules to form the three-dimensional network.     

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.     

Synthesis and physicochemical study of diazabicycloundecene hexamolybdochromate [C9H16N2]H3[CrMo6O18(OH)6] · 2H2O

Quinazoline hexamolybdochromate [C₉H₁₆N₂]H₃[CrMo₆O₁₈(OH)₆] · 2H₂O has been synthesized and studied by mass spectroscopy, X-ray powder diffraction, thermogravimetry, and IR and NMR spectroscopy. The compound crystallizes in triclinic system with the unit cell parameters a = 15.06 Å, b = 13.08 Å, c = 8.17 Å, α = 59.85°, β = 123.15°, γ = 107.01°, V = 1165.62 ų, ρ_pycn = 3.58 g/cm³, and Z = 2.     

Synthesis,Crystal Structure and Vibrational Spectroscopy of NH4[Co(NH3)5(H2O)][B4O5(OH)4]2·6H2O

A novel hydrated cobalt tetraborate complex NH₄[Co(NH₃)₅(H₂O)][B₄O₅(OH)₄]₂·6H₂O, was synthesized by the reaction of NH₄‐borate aqueous with CoCl₂ and its structure was determined by single crystal X‐ray diffraction. The crystal system of this complex is orthorhombic, the space group is Pnma, and the unit cell parameters are a=1.2901(2) nm, b=1.6817(3) nm, c=1.1368(2) nm, α=β=γ=90°, V=2.4742(8) nm³, and Z=4. This compound contains infinite borate layers constructed from [B₄O₅(OH)₄]^2? units via hydrogen bonds. The adjacent polyborate anion layers are further linked together with the octahedral [Co(NH₃)₅(H₂O)]³⁺ groups through hydrogen bonds to form 3D framework. The groups and guest water molecules are deposited in the empty space of this framework and interact with the layers by extensive hydrogen bonds. Infrared and Raman spectra (4000–400 cm^?1) of NH₄[Co(NH₃)₅(H₂O)][B₄O₅(OH)₄]₂·6H₂O were recorded at room temperature and analyzed. Fundamental vibrational modes were identified and band assignments were made. The middle band observed at 575 cm^?1 in Raman spectrum is the pulse vibration of [B₄O₅(OH)₄]^2?.     

Synthesis and crystal structures of yttrium sulfates Y(OH)(SO4), Y(SO4)F,YNi(OH)3(SO4)-II and Y2Cu(OH)3(SO4)2F·H2O

Y(OH)(SO₄), Y(SO₄)F, YNi(OH)₃(SO₄)-II and Y₂Cu(OH)₃(SO₄)₂F·H₂O are obtained from hydrothermal reactions at 380°C under a pressure of 210 MPa. Their crystal structures were refined from single-crystal X-ray diffraction data. The four compounds have the following space groups and unit cells: Y(OH)(SO₄), P2₁/n, a=7.9498(6), b=10.9530(9), c=8.1447(6) Å, β=93.764(1)°; Y(SO₄)F, Pnma, a=8.3128(9), b=6.9255(7), c=6.3905(7) Å; YNi(OH)₃(SO₄)-II, Pnma, a=6.9695(8), b=7.2615(8), c=10.292(1) Å; Y₂Cu(OH)₃(SO₄)₂F·H₂O, P2₁/n, a=11.6889(7), b=6.8660(4), c=12.5280(8) Å, β=97.092(1)°. The coordination environments of the yttrium atoms in the four structures vary from highly irregular 6+2, 6+3, 7+1 coordination polyhedra to relatively regular dodecahedra.     

Magnetic Properties of (C5H6N)5[Fe13O4F24(OCH3)12] · CH3OH · 4H2O

The static magnetic susceptibility of Fe(III) complex [Fe₁₃O₄F₂₄(OCH₃)₁₂]^5– was measured in the temperature range 2–300 K. The structure of the complex consists of four triangular Fe₃ fragments interacting with a central Fe atom. By disregarding weak exchange interactions through F bridges, an analytical solution of the exchange Hamiltonian was obtained with Nf 1.3 × 10¹⁰ levels. This made it possible to perform quantitative interpretation of the temperature dependence of the magnetic susceptibility. The obtained exchange parameters of the best approximation are –2J ₁ = 43 cm^–1, –2J ₂ 30 cm^–1. The ratio J ₂/J ₁ 0.70 suggests that the Fe₁₃ ground state has the spin of the ground state 23/2 or 15/2.     

Syntheses and structures of nine-coordinate NH4[HoIII(Edta)(H2O)3] · 1.5H2O, (NH4)4[Ho 2 III (Dtpa)2] · 9H2O, and (NH4)3[HoIII(Ttha)] · 5H2O complexes

The three title complexes, NH₄[Ho^III(Edta)(H₂O)₃] · 1.5H₂O (I) (H₄Edta = ethylenedianine-N,N,N′,N′-tetraacetic acid), (NH₄)₄[Ho ₂ ^III (Dtpa)₂] · 9H₂O (II) (H₅Dtpa = diethylenetriamine-N,N,N′,N″,N″-entaacetic acid), and (NH₄)₃[Ho^III(Ttha)] · 5H₂O (III) (H₆ Ttha = triethylenetetramine-N,N,N′,N″,N?,N?-hexaacetic acid), have been prepared and characterized by FT-IR, elemental analyses, and single-crystal X-ray diffraction technique. Complex I has a nine-coordinate mononuclear structure with distorted monocapped square antiprismatic conformation and its crystal structure belongs to orthorhombic system and Fdd2 space group. The crystal data are as follows: a = 19.343(9), b = 35.125(17), c = 12.364(6) Å, V = 8400(7) ų, Z = 16, M = 552.26, ρ_calcd = 1.747 g cm^?3 μ = 3.828 mm^?1, and F(000) = 4368. Complex II has a binuclear nine-coordinate pseudomonocapped square antiprismatic conformation and its crystal structure belongs to triclinic system and space P1 group. The crystal data are as follows: a = 9.7637(16), b = 9.9722(16), c = 12.945(2) Å, α= 85.853(2)°, β = 77. 140(2)°, γ = 77.140(2)°, V = 1198.4(3) ų, Z = 1, M = 1340.80, ρ_calcd = 1.858 g cm^?3, μ = 3.380 mm^?1, and F(000) = 674. As for complex III, it also has nine-coordinate mononuclear structure with distorted tricapped trigonal prism and its crystal structure belongs to monoclinic system andP2₁/c space group. The crystal data are as follows: a = 10.349(3), b = 12.760(4), c = 23.142(7) Å, β = 91.020(6)°, V = 3055.6(16) ų, Z = 2, M = 797.55, ρ_calcd = 1.734 g cm^?3, μ = 2.674 mm^?1, and F(000) = 1624. The results showed that although the ligands are different from one another in the shape and the numbers of coordination atoms, they all have nine-coordinate structures. However, one of them has binuclear structure and the other two have mononuclear structures because of the difference of the ligands.     

Synthesis of calcium titanate from [Ca(H2O)3]2[Ti2(O2)2O(NC6H6O6)2]·2H2O as a cheap single-source precursor

Calcium titanate (CaTiO₃) was conveniently synthesized by thermal decomposition of a single-source precursor [Ca(H₂O)₃]₂[Ti₂(O₂)₂O(NC₆H₆O₆)₂]·2H₂O at low temperature. This single-source precursor was characterized by elemental analysis, IR spectrum, thermal gravimetric analysis and X-ray single crystal diffraction. The calcined products at different temperature were further characterized by powder X-ray diffractions and IR spectra. The morphology, microstructure, and crystallinity of the resulting CaTiO₃ materials have been characterized by SEM and TEM. The BET measurement revealed that the CaTiO₃ powders had a surface area of 14.0 m²/g. In addition, the microwave dielectric properties of the resulting CaTiO₃ material have been measured.     

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.     

PREPARATION AND STRUCTURE OF TETRAMETHYLAMMONIUM HYDROGEN TRIPEROXOTRIMOLYBDODISULFATE TRIHYDRATE, [N(CH3)4]3[H(SO4)2-(MoO2(O2))3]· 3H2O

Abstract

A novel peroxopolyoxomolybdate compound, [N(CH₃)₄]₃ [H(SO₄)₂ (MoO₂(O₂))₃] · 3H₂O, has been obtained from a strongly acidic aqueous solution of a molybdate-sulfate system as the monoclinic crystal of P2/n, a = 13.497(3), b = 15.231(4), c = 32.603(2) Å, β = 103.113(9)°, and V = 6577(2) ų. The final R-value was 0.0986 for 395 parameters using 7162 reflections. Each of the two crystallographically independent polyanions contains three molybdenum atoms with five O^2?, one O₂ ^2?, and two sulfate groups, one of which is a tripod ligand apical to the molybdenum plane, and the other is a bipod ligand equatorial to the Mo plane.     

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