Synthesis, structural characterization and properties of a 3D infinitely extended structural rare earth coordination compound of K3{[Sm(H2O)7]2Na[α-SiW11O39Sm(H2O)4]2} · 14 H2O· 14 H2O

A 3D infinitely extended structural rare earth coordination compound with a formula of K₃{[Sm(H₂O)₇]₂Na[α-SiW₁₁O₃₉Sm(H₂O)₄]₂}·14H₂O has been synthesized by reaction of Sm₂O₃, HClO₄, NaOH with α-K₈SiW₁₁O39·nH₂O, and characterized by IR, UV spectra, ICP, TG-DTA, cyclic voltammetry, variable-temperature magnetic susceptibility and X-ray single-crystal diffraction. X-ray single-crystal diffraction indicates that the title compound crystallizes in a triclinic lattice, Pī space group, with a = 1.2462(3) nm, b = 1.2652(3) nm, c = 1.8420(4) nm, α = 87.45(3)°, β = 79.91(3)°, γ= 82.57(3)°, Z = 1, R₁ = 0.0778, wR₂ = 0.1610. Structural analysis reveals that Sm³⁺(1) coordination cation has incorporated into the vacant site of [α-SiW11O₃₉]⁸⁻ entity, forming the [α- SiW₁₁O₃₉Sm(H₂O)₄]⁵⁻ subunit. The two adjacent [α-SiW₁₁O₃9Sm(H₂O)4]⁵⁻ subunits are combined with each other through two Sm(1)-O-W bridges accompanying the formation of dimmer structural unit [α-SiW₁₁O₃₉Sm(H₂O)₄]₂ ¹⁰⁻ of the title compound. The neighboring dimmer structural units [α-SiW₁₁O₃₉Sm(H₂O)₄]₂ ¹⁰⁻ are linked to form the 1D chainlike structure by means of two Sm³⁺(2) and a Na⁺(1) coordination cations. The K⁺(1) cations connect the 1D packing chains constructing the 2D netlike structure, and adjacent netlike layers are also grafted by K⁺(2) cations to build the novel 3D infinitely extended structure. The result of TG-DTA curves manifests that the decomposition temperature of the title polyanionic framework is 554°C. The cyclic voltammetry measurements show that the title polyanion has the two-step redox processes in aqueous solution with pH = 3.1. Variable temperature magnetic susceptibility indicates the title compound obeys the Cruie-Weiss Law in the higher temperature range from 110 to 300 K, while in the lower temperature range from 2 to 110 K the comparatively strong antiferromagnetism interactions can be observed.     

Crystal and molecular structures of the Rh[(C2H5O)2PS2]3 and Co[(C6H5O)2PS2]3 chelate compounds

The crystal structures of the Rh[(EtO)₂PS₂]₃ (I) and Co[(PhO)₂PS₂]₃ (II) chelate compounds were determined from X-ray diffraction (XRD) data (CAD-4 diffractometer, MoK _β radiation, 1193 F _hkl , R = 0.0516 for I and 513 F _hkl , R = 0.0305 for II). Crystals I are monoclinic: a = 14.233(3) Å, b = 13.570(3) Å, c = 14.272(3) Å; β = 90.66(3)°, V = 2756.3(10) ų, Z = 4, ρ_calc = 1.587 g/cm³, space group C2/c. Crystals II are trigonal: a = 15.149(2) Å, c = 30.306(6) Å; V = 6023.2(16) ų, Z = 6, ρ_calc = 1.493 g/cm³, space group R3ˉ. Structures I and II consist of discrete mononuclear molecules. The coordination polyhedra of the M atoms (M = Rh, Co) are distorted octahedra formed by six sulfur atoms of three cyclic bidentate (RO)₂ PS₂⁻ ligands. Original Russian Text Copyright ? 2008 by R. F. Klevtsova, L. A. Glinskaya, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 2, pp. 330–334, March–April, 2008.     

Structure of uranyl complexes with acetylenedicarboxylic acid, K(H5O2)[UO2(OOCC≡CCOO)2 · H2O] · 2H2O and Cs2[UO2(OOCC≡CCOO)2 · H2O] · 2H2O

Uranyl complexes with acetylenedicarboxylic acid, K(H₅O₂)[UO₂L₂H₂O] · 2H₂O (I) and Cs₂[UO₂L₂H₂O] · 2H₂O (II), L²⁻ = C₄O ₄ ²⁻ were prepared for the first time. The composition and structure of the complexes were determined by X-ray diffraction. The crystal data are as follows: a = 16.254(12) ?, b = 13.508(8) ?, c = 7.683(6) ?, β = 90.91(7)°, space group C2/c, V = 1687(2) ?³ (I); a = 7.0745(10), b = 18.4246(10), c = 13.1383(10) ?, space group Abm2, V = 1712.5(3) ?³ (II). The structures of I and II are based on [UO₂L₂H₂O] _n ²⁻ anionic chains stretched along the [101] direction (I) or [010] direction (II). In I and II, the uranium coordination polyhedron is a pentagonal bipyramid in which the equatorial environment of the uranyl ions is formed by the oxygen atoms of the four L²⁻ anions and the water molecule. The L²⁻ anions in I and II are bidentate bridging ligands connecting two uranium atoms that are next to each other in the anionic chain; their coordination capacity is equal to 2. In I, the K⁺ and H₅O ₂ ⁺ cations are outer-sphere species. The latter form hydrogen bonds combining the anionic chains shifted by translation b with respect to each other. The [UO₂L₂H₂O] _n ²⁻ chains in I are surrounded by the potassium and oxonium cations; in II, these are combined by hydrogen bonds into anionic layers between which Cs⁺ cations are arranged. The IR spectrum of compound II was measured and interpreted. Original Russian Text ? I.A. Charushnikova, A.M. Fedoseev, N.A. Budantseva, I.N. Polyakova, Ph. Moisy, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 1, pp. 63–69.     

Protonation of the acyclic tetraaza metallocomplex of gold(III) [Au(C9H19N4)]2+ in aqueous solution. Synthesis and crystal and molecular structure of [Au(C9H20N4)](H5O2)(ClO4)4

Protonation equilibrium has been studied for the acyclic gold(III) tetraaza metallocomplex [AuB]²⁺ [B = N, N′-bis(2-aminoethyl)-2,4-pentanediiminato(1−)] in aqueous solution. The synthetic procedure is described. The crystal and molecular structure of the protonated form of the [AuHB](H₅O₂)(ClO₄)₄ complex has been determined. Monoclinic crystals with unit cell dimensions a = 11.964(2) Å, b = 13.789(3) Å, c = 15.496(3) Å, β = 109.00(3)°, V = 2417.1(8) ų, Z = 4, ρcalc = 2.243 g/cm³, space group P2₁/n. The structure is built of nearly planar [Au(C₉H₂₀N₄)]³⁺ complex cations, (H₅O₂)⁺ cations, and [ClO₄]⁻ anions. The gold atom coordinates four nitrogen atoms of the ligand, forming a square plane. The six-membered chelate ring of the ligand is protonated at the central β-carbon atom and contains imine C=N bonds. The oxygen atoms of the perchlorate ions are hydrogen bonded to the (H₅O₂)⁺ dihydroxonium ion and to the nitrogen atoms of the NH₂ groups of the [AuHB]³⁺ cation. Original Russian Text Copyright ? 2005 by V. A. Afanasieva, L. A. Glinskaya, R. F. Klevtsova, and I. V. Mironov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 5, pp. 909–915, September–October, 2005.     

Crystal and molecular structures of Ni[(iso-C4H9)2PS2]2 and Pd[(iso-C4H9)2PS2]2 chelates

Crystal structures of chelate compounds Ni[(iso-C₄H₉)₂PS₂]₂ (I) and Pd[(iso-C₄H₉)₂PS₂]₂ (II) have been determined by X-ray diffraction: diffractometer X8-APEX, MoK _α∔ -radiation, 1048 F _hkl , R = 0.0544 for I and CAD-4 diffractometer, MoK _α∔ -radiation, 1283 F _hkl , R = 0.0347 for II. The crystals are rhombic: a = 12.921(5) Å, b = 17.094(5) Å, c = 22.971(5) Å; V = 5074(3) ų, Z = 8, calc = 1.250 g/cm³, space group Pbca for I and a = 13.312(3) Å, b = 16.130(7) Å, c = 23.171(5) Å; V = 4975(3) ų, Z = 8, ρ_calc = 1. 208 g/cm³, space group Pbca for II. The structures of I and II are formed by discrete mononuclear molecules. Coordination cores MS₄ (M = Ni, Pd) approach planar square configurations. Original Russian Text Copyright ? 2005 by L. A. Glinskaya, T. G. Leonova, T. E. Kokina, R. F. Klevtsova, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 4, pp. 715–720, July–August, 2005.     

Structure of [RuNO(NH3)3(H2O)Cl](NO3)2, product of interaction between hydroxonitrotriamminenitrosoruthenium(II) chloride and nitric acid

The structure of the product formed on boiling [RuNO(NH₃)₃(NO₂)(OH)]Cl·0.5H₂O in 3 M HNO₃ is determined by XRD. The crystals belong to monoclinic symmetry. Crystallographic data for H₁₁ClN₆O₈Ru are: a = 13.7924(4) ?, b = 6.9114(2) ?, c = 12.3577(4) ?, β = 111.863(1)°, V = 1093.27(6) ?³, Z = 4, d _calc = 2.185 g/cm³, space group Cc. The structure is built of complex [RuNO(NH₃)₃(H₂O)Cl]²⁺ cations and NO₃⁻ anions. The compound is studied by IR spectroscopy and X-ray phase analysis. Original Russian Text Copyright ? 2009 by V. A. Emel’yanov, E. V. Kabin, and I. A. Baidina __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 3, pp. 598–601, May–June, 2009.     

Crystal and molecular structure of the [Y(Phen){( i -C4H9)2PS2}2NO3] mixed-ligand compound

The [Y(Phen){(i-C₄H₉)₂PS₂}₂NO₃] mixed-ligand compound (I) was synthesized. Its structure was determined by X-ray diffraction analysis (X8 APEX diffractometer, λMoK _α , 3788 F _hkl , R = 0.0677). Crystals I are orthorhombic: a = 10.6495(8) Å, b = 20.006(2) Å, c = 35.317(4) Å, V = 7524.4(13) ų, Z = 8, ρ_calc = 1.324 g/cm³, space group Pbca. The structure is built of mononuclear discrete molecules. The N₂O₂S₄ coordination polyhedron of the Y atom is a distorted dodecahedron. Original Russian Text Copyright ? 2008 by V. L. Varand, L. A. Glinskaya, R. F. Klevtsova, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 1, pp. 182–186, January–February, 2008.     

Crystal and molecular structure of (NH4)2[UO2(NO3)4] and [(NH4)(18C6)]2[UO2(NO3)4]

Single crystals of diammonium tetranitratouranylate (NH₄)₂[UO₂(NO₃)₄] (I) and a new diammonium tetranitratouranylate complex with 18-crown-6 [(NH₄)(18C6)]₂[UO₂(NO₃)₄] (II) have been synthesized by the reaction of diaquadinitratouranyl tetrahydrate with ammonium nitrate in a nitric acid solution and the reaction of the same reagents with 18C6 in an ethanol solution, respectively. The X-ray diffraction analysis of compounds I and II has been performed. Crystals of compounds I and II are monoclinic, Z = 2, space group P2₁/n, a = 6.4075(5) ?, b = 7.7851(7) ?, c = 12.4461(12) ?, β = 101.239(1)°, V = 608. 94(9) ?³ for compound I and a = 10.542(9) ?, b = 8.590(8) ?, c = 22.5019(19) ?, β = 101.632(1)°, V = 2058.3(3) ?³ for compound II. The [UO₂(NO₃)₄]²⁻ complex anion in compounds I and II contains two monodentate and two bidentate cyclic nitrato groups, and the coordination number of uranyl is 6. The 18C6 molecule in the structure of compound II has the classic crown conformation and combined with the ammonium ion by three hydrogen bonds. Compounds I and II formed by electrostatic attraction forces between counterions are stabilized by (NH₄⁺)NH...O(NO₃⁻) interionic hydrogen bonds.     

Synthesis and study of (CN3H6)2[(UO2)2(C2O4)(SeO3)2] by IR spectroscopy and X-ray diffraction

Single crystals of (CN₃H₆)₂[(UO₂)₂(C₂O₄)(SeO₃)₂] were synthesized and studied by IR spectroscopy and X-ray diffraction. The compound crystallizes in the triclinic system with the unit cell parameters a = 7.1169(12) ?, b = 7.4874(10) ?, c = 8.9748(14) ?, α = 88.243(6)°, β = 74.546(6)°, γ = 81.445(6)°, space group P[`1]P\bar 1, Z = 1, R = 0.0304. The main structural units of the crystals are layers of the [(UO₂)₂(C₂O₄)(SeO₃)₂]²⁻ composition; the layers belong to the crystal chemical group A ₂ K ⁰² T ₂³ (A = UO₂²⁺ K ⁰² = C₂O₄²⁻, T ³ = SeO₃^–) of uranyl complexes. Uranium-containing complex groups are linked by electrostatic interactions and a network of hydrogen bonds with CN₃H₆⁺ guanidinium ions to form a three-dimensional framework.     

2∞[Yb2(NH2)2( Pz )4][Yb(NH3)2( Pz )3 Pz H]: Electride Induced Synthesis of a 2D-Ytterbium-Pyrazolate Network

Summary. ² _∞[Yb₂(NH₂)₂(Pz)₄][Yb(NH₃)₂(Pz)₃ PzH], Pz ⁻ = pyrazolate anion, PzH = pyrazole, C₃H₄N₂ is obtained by the reaction of ytterbium metal with pyrazole in liquid ammonia and subsequent increase of the temperature to 200°C resulting in the formation of colorless single crystals of the compound. The X-ray single crystal analysis reveals that the structure consists of ² _∞[Yb₂(NH₂)₂(Pz)₄] planes with neutral [Yb(NH₃)₂(Pz)₃ PzH] monomeric molecules that are located between the planes and ytterbium is trivalent. This is the first example of a two-dimensional network structure of an organic amine of the rare earth elements that derives from an electride induced synthesis. The product decomposes under release of ammonia outside its sealed reaction vessel, viz. if the NH₃ pressure is removed.     

Synthesis of heteroligand complex Nd(Phen){( iso -C4H9)2PS2}2(NO3). Crystal structure of [Nd(Phen){( iso -C4H9)2PS2}3] and luminescent properties of these compounds

The heteroligand complex Nd(Phen){(iso-C₄H₉)₂PS₂}₂(NO₃) (I) was synthesized and its IR spectrum was analyzed. The anions (iso-C₄H₉)₂PS_2/− and N_3/− act as bidentate cyclic ligands. The single crystals of [Nd(Phen){iso-C₄H₉)₂PS₂}₃] (II) were obtained on evaporation of a solution of complex I in a mixture CH₂Cl₂-hexane and were studied by X-ray diffraction. Crystals II are triclinic: a = 10.5509(5); b = 14.7432(8), c = 16.8503(10) ?; α = 102.882(2)°, β = 97.211(2)°, γ= 108.087(2)°, V = 2374(2) ?³, Z = 2, ρ(calcd.) = 1.332 g/cm³, space group . The coordination polyhedron of the Nd atom in a separate mononuclear molecule II is a distorted dodecahedron N₂S₆. The molecules are bound by weak van der Waals and π-π interactions. The photoluminescence spectra of complexes I, II were measured and interpreted. Original Russian Text ? S.V. Larionov, V.L. Varand, R.F. Klevtsova, T.G. Leonova, L.A. Glinskaya, E.M. Uskov, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 12, pp. 944–950.     

Crystal structure of [Mn(1,10-C12H8N2)3](B6H7)2

A new compound [MN^II(Phen)₃]²⁺(B₆H₇)₂⁻ is synthesized; its crystal structure is studied by XRD at 100 K. Crystallographic data: C₃₆H₃₈B₁₂N₆Mn, M = 739.39, triclinic symmetry, space group P , unit cell parameters: a = 10.3131(3) ?, b = 13.4839(4) ?, c = 15.1132(4) ?; α = 97.696(1)°, β = 108.324(1)°, γ = 102.211(1)°; V = 1903.9(1) ?³, Z = 2, d _calc = 1.290 g/cm³. The structure is solved by direct and Fourier methods and refined by full-matrix LSM in the anisotropic (isotropic for hydrogen atoms) approximation to the final factor R ₁ = 0.036 for 10169 I _hkl ≥ 2σ _I (Bruker-Nonius X8 APEX CCD diffractometer, λMoK _α). The structure contains two crystallographically different anions. Original Russian Text Copyright ? 2009 by T. M. Polyanskaya, M. K. Drozdova, V. V. Volkov, and K. G. Myakishev __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 2, pp. 381–385, March–April, 2009.     

Syntheses, Crystal Structures and Third-order Nonlinear Optical Properties of Coordination Polymers {[Et4N][Ag2I3]}n and [CuBr(C10H8N2S2)]n

Coordination polymers {[Et₄N][Ag₂I₃]}_n (1) and [CuBr(C₁₀H₈N₂S₂)]_n (2) were prepared by standard Schlenk techniques. Their X-ray measurements indicate that polymer (1) crystallizes in the orthorhombic space group Pnma, and polymer (2) crystallizes in the monoclinic space group P21/n. Complex (1) has a hanging ladder-like polymeric chain which can also be described as a helical chain bridged by Ag–Ag edges. Complex (2) exhibits a monoclinic crystal system with a slightly distorted tetrahedron. The nonlinear optical (NLO) properties of (1) and (2) were investigated by using Z-scan techniques with an 8 ns pulsed laser at 532 nm. These two coordination polymers exhibit NLO absorption and an effective self-focusing effect. The effective α₂ and n₂ values of cluster (1) are 3.04×10⁻¹¹ m W⁻¹ and 7.6×10⁻¹⁸ m² w⁻¹ and the effective α₂ and n₂ values of compound (2) are 1.08×10⁻¹¹ m W⁻¹ and 3.1×10⁻¹⁸ m² w⁻¹ when measured in CH₂Cl₂ solution.     

Synthesis, crystal structure and photoluminescence of a novel tetra-nuclear calcium complex [(Ca(C15H8O7S)-(H2O)(DMSO))3(Ca(C15H8O7S) (DMSO)2]·4DMSO

The sulfonate derivate of chrysin coordinates with Ca²⁺ to form a novel tetra-nuclear calcium complex [(Ca(C₁₅H₈O₇S)(H₂O)(DMSO)₃(Ca(C₁₅H₈O₇S)(DMSO)₂]·4DMSO. The structure of the complex is characterized by IR,¹H NMR and X-ray single-crystal diffraction analysis. The results show that the complex crystallizes in triclinic, space group PĪ, cell parametera = 1.4725(6) nm,b = 1.6480(7) nm,c = 2.1006(8) nm, α = 83.928(7)°, β= 85.938(7)°, γ= 85.212(7)°,V = 5.041(3) nm³,Dc = 1.476 g/cm³,Z = 2, μ=0.568 nm⁻¹,F(000) = 2324,R = 0.0778,wR = 0.1821. In the complex, four Ca²⁺ which are bridged by four 5-hydroxyanion-7-dihydro-xyfla-vone-6-sulfonate ligands with their carbonyl and 5-hydroxyanion group build an approximate square. The coordination number of Ca²⁺ is 7 and the coordinated atoms are all oxygen from the carbonyl, hydroxyl and suflo-group of 5-hydroxyanion-7-hydroxyflavone-6-sulfonate, H₂O and DMSO. Four ligands locate on two sides of the square. Two of them on the same side are almost paralleled and aromatic п-п stacking exists between them. Ligands on the opposite side are nearly perpendicular to each other. Meanwhile, the solid of title compound has the photoluminescent phenomenon. The title compound emits green fluorescence (λ_em = 520 nm) when it is excited at the wavelength of 410 nm and its photoluminescent mechanism is discussed.     

Heterometallic clusters with the {MoNbI8} core: The synthesis and crystal structures of (Ph4P)2[Mo5NbI8Cl6] and (4-MePyH)5[Mo5NbI8Cl6]Cl2

Heterometallic chloride complexes [Mo₅NbI₈Cl₆] ⁿ⁻ (n = 2, 3) are synthesized. The crystal structures of their salts are determined: for (Ph₄P)₂[Mo₅NbI₈Cl₆] (I), triclinic crystal system, spacegroup P [`1]\bar 1, a = 10.9886(6), b = 11.4604(5), c = 13.4343(7) ?, α = 66.124(2), β = 86.892(2), γ = 86.490(2)°, Z = 1, V = 1543.35(13) ?³; and for (4-MePyH)₅[Mo₅NbI₈Cl₆]Cl₂ (II), monoclinic crystal system, space group C2/m, a = 16.4937(4), b = 14.7335(3), c = 11.6534(3) ?, β = 99.8750(10)°, Z = 2, V = 2789.94(11) ? The geometric parameters of compounds I and II and the conditions for the formation of the complexes with the charges −2 and −3 are discussed.     

Synthesis, crystal structure and characterization of a 2-D network organic-inorganic hybrid polymer with [α-BW12O40]5? as building blocks

A two-dimensional network compound [Ce(DMF)₄(H₂O)][α-BW₁₂O₄₀]·H₂O·(HDMA)₂ (HDMA = protoned dimethylamine, DMF = N,N-dimethylformamide) was synthesized from α-H₅BW₁₂O₄₀·nH₂O, Ce(NO₃)₃·6H₂O and DMF and characterized by IR, UV spectra and TG-DTA. The result of the X-ray single crystal diffraction indicates that the crystal is monoclinic, space group P2₁/n, with unit cell dimensional: a = 1.1983(3), b = 2.4216(5), c = 1.9517(4) nm, β = 92.91(3)°, Z = 4, R ₁ = 0.07710, wR ₂ = 0.1416. Structural analysis indicates that every [Ce(DMF)₄(H₂O)]³⁺ building block is surrounded by three adjacent [α-BW₁₂O₄₀]⁵⁻ polyanions, meanwhile, every [α-BW₁₂O₄₀]⁵⁻ polyanion interconnects with three neighboring [Ce(DMF)₄(H₂O)]³⁺ subunits, by making use of which two-dimensional network structure can be constructed. The result of thermogravimetric analysis manifests that the title compound has two-stage weight loss and the decomposition temperature of the title polyanionic framework is 560°C. The electrochemical analysis shows the title polyanion has three-step redox processes in the pH = 4–7 media.     

Heteropoly Complexes Na0.5Cs2 ? x[H0.5 ? xM

Crystals of novel heterepoly complexes (HPC) Na_0.5Cs_{2 − x} [H_{0.5 − x} M _x ^II X^III(OH)₆Mo₆O₁₈] · 7−8H₂O (M^II = Fe, Mn; X^III = Cr, Al) are synthesized. Crystal structures of the complexes Na_0.5Cs_{2 − x} [H_{0.5 − x} Fe_xCr(OH)₆Mo₆O₁₈] · 7H₂O (I) (x = 0.19) and Na_0.5Cs_{2 − x} [H_{0.5 − x} Mn_xAl(OH)₆Mo₆O₁₈] · 8H₂O (II) (x = 0.22) are determined (space group Pbcn, Z = 8, a = 23.023(4) Å, b = 22.064(4) Å, c = 11.606(3) Å, V = 5895.66 ų for I and a = 22.972(9) Å, b = 22.002(8) Å, c = 11.543(5) Å, V = 5834.18 ų for II, respectively). The [X^III(OH)₆Mo₆O₁₈]³⁻ ligands were found to be coordinated in monodentate fashion to M atoms due to the participation of a terminal O atom of the cis-MoO₂ group in coordination with the Fe and Mn atoms, which was confirmed by IR data. __________ Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 9, 2005, pp. 663–676. Original Russian Text Copyright ? 2005 by Gavrilova, Molchanov.     

A Novel Dimeric Polyoxotungstate Decorated by 3d-4f atoms: K4LaH[As2W20CuO67 (H2O)3]Cl2· 22.5H2O

A novel dimeric polyoxotungstate K₄LaH[As₂W₂₀CuO₆₇(H₂O)₃ ]Cl₂·22.5H₂O has been synthesized and characterized by IR, element analysis TG and cyclic voltammogram. The anion K₄LaH[As₂W₂₀CuO₆₇(H₂O) ₃]Cl₂·22.5H₂O can be characterized as two {As^IIIW₉O₃₃}⁹⁻ moieties linked via a {Cu(OH)}, a {W(H₂O)} and a {WO(H₂O)} group which total coordination numbers are respectively 5, 5, 6. An additional lanthanide atom connects the dimeric cluster via a W-O-La bond. The X-ray single crystal diffraction shows that it is in the triclinic system, space group P-1, with a = 12.287(6) ?, b = 20.197(1) ?,c=21.483(1)?,α = 62.584(8)°,β = 74.659(8)°,γ = 75.273(9)°,V = 4509(4)?³, Z = 2. To our known, the polyoxotungstate is the novel sandwich-type polyoxoanion, which is decorated by transition-metal and lanthanide atoms at the same time.     

Synthesis and crystal and molecular structure of CdPhen( iso -C4H9OCS2)2 and CdPhen( n -C4H9OCS2)2 mixed-ligand complexes

Mixed-ligand complexes CdPhen(i-BuOCS₂)₂ (I) and CdPhen(n-BuOCS₂)₂ (II) have been synthesized. Their structures were solved using X-ray diffraction data (X8 APEX diffractometer, MoK _α radiation, 1641 and 2497 F _hkl , R = 0.0359 and 0.0389). Crystals I are orthorhombic with unit cell parameters a = 6.5883(3) Å, b = 19.7123(10) Å, c = 20.1936(11) Å, V = 2622.6(2) ų; Z = 4, space group Pbcn; crystals II are monoclinic, a = 6.5845(2) Å, b = 19.1522(6) Å, c = 20.7091(7) Å, β = 97.106(1), V = 2591.5(1) ų, Z = 4, space group C2/c. The structures consist of discrete mononuclear molecules in which the coordination polyhedron of the Cd atom is a distorted N₂S₄ octahedron. Molecular packing and interactions in the structures are discussed. Original Russian Text Copyright ? 2007 by R. F. Klevtsova, T. G. Leonova, L. A. Glinskaya, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No. 2, pp. 274–281, March–April, 2007.