Synthesis, spectroscopic characterisation and X-ray structure of [trans-Co(en)2(NO2)2]2(Cr2O7)

Dark red crystals of bis[trans-dinitrobis(ethylenediamine)cobalt(III)] dichromate, [trans-Co(en)₂(NO₂)₂]₂(Cr₂O₇) have been obtained by slowly allowing to mix the solutions of potassium dichromate and trans-dinitrobis(ethylenediamine)cobalt(III) nitrate in 1:2 molar ratio in aqueous medium. Elemental analyses and spectroscopic techniques (IR, UV/visible, ¹H and ¹³C NMR) were used for characterizing the complex salt. The complex salt crystallizes in the orthorhombic space group Fdd2 with unit cell dimensions a = 24.778(2) ?, b = 30.457(2) ?, c = 6.5364(5) ?, Z = 8, V = 4932.8(7) ?³, R₁ = 0.0617 and wR₂ = 0.1518. X-ray structure determination revealed an ionic structure consisting of cationic cobaltammine [trans-Co(en)₂(NO₂)₂]NO₃ and dichromate anion. It is the first crystal structure of this cation with a dianion.     

The structure of the scandium iodide complex with antipyrine (AP) and its comparison with the structure of nonisostructural analogues (Compounds [Ln(AP)6]I3 (Ln = La, Y, or Eu))

An X-ray diffraction study of the scandium iodide complex with antipyrine [Sc(AP)₆]I₃ (AP is antipyrine, i.e., 2,3-dimethyl-1-phenyl-3-pyrazolin-5-one) (I), which is not isostructural to the analogous compounds of Y, La, and Eu (II), is performed. Crystals I are trigonal; a = 24.911 ? and c = 10.140 ?; Z = 3, space group P $ \bar 3 $ \bar 3 . Crystal I is built of [Sc(AP)₆]³⁺ complex cations of two types and I⁻ anions. In both cations, the Sc atom is octahedrally coordinated by six O atoms of six AP ligands (Sc-O, 2.054–2.078 ?). Complexes I differ from II by the absence of π-π stacking interactions between AP molecules, resulting in a supramolecular cation. Complex cations I of both types form combined layers. All I⁻ anions are located in the interlayer space, being statistically disordered within a flat area limited by eight complex cations of Sc1 and Sc2.     

A novel representative {[Rb1.94(H2O,OH)3.84](H2O)0.1}{Al4(OH)4[PO4]3} in the pharmacosiderite structure type

The crystal structure of a new synthetic aluminophosphate {[Rb_1.94(H₂O,OH)_3.84](H₂O)_0.1}{Al₄(OH)₄[PO₄]₃} synthesized under mild hydrothermal conditions (T = 280°C, P = 100 atm) in the Rb₂O-Al₂O₃-P₂O₅-H₂O system is determined using X-ray diffraction (Stoe IPDS diffractometer, λMoK _α, graphite monochromator, 2θ_max = 64.33°, R = 0.032 for 312 reflections). The main crystal data are as follows: a = 7.4931(6) ?, space group P 3m, Z = 1, and ρ_calcd = 2.76 g/cm³. It is shown that the synthesized compound belongs to the pharmacosiderite structure type with a characteristic mixed open microporous framework composed of octahedra and tetrahedra. A comparative crystal chemical analysis of related phases is performed, and the chemical compositions of promising absorbents, i.e., hypothetical compounds potentially possible in the structure type under consideration, are proposed. It is established that pharmacosiderite and rhodizite are homeotypic to each other. Original Russian Text ? O.V. Yakubovich, W. Massa, O.V. Dimitrova, 2008, published in Kristallografiya, 2008, Vol. 53, No. 3, pp. 442–449.     

Crystal structure of M4[(UO2)2C2O4(SO4)2(NCS)2] ( M = K+, Rh+) and K4[(UO2)2C2O4(SeO4)2(NCS)2]

Three heteroacidoligand uranyl complexes M ₄[(UO₂)₂C₂O₄(SO₄)₂(NCS)₂] (M = K⁺ (I), Rb⁺ (II)) and K₄[(UO₂)₂C₂O₄(SeO₄)₂(NCS)₂] (III) have been synthesized and their crystal structure has been determined by X-ray diffraction analysis. The compounds I–III are isostructural and crystallized in the monoclinic system, sp. gr. P2₁/c, Z = 2, a = 11.5548(3) ?, b = 7.0847(1) ?, c = 13.5172(3) ?, β = 93.130(1)°, V = 1104.90(4), R = 0.015 (I); a = 11.5854(9) ?, b = 7.3841(6) ?, c = 13.9072(9) ?, β = 95.754(3)°, V = 1183.74(15), R = 0.0235 (II); a = 11.6715(3) ?, b = 7.1418(2) ?, c = 13.8546(1) ?, β = 93.539(1)°, V = 1152.66(5), R = 0.0126 (III). Basic structural units of these crystals are [(UO₂)₂C₂O₄(XO₄)₂(NCS)₂]⁴⁻ chains, which belong to the crystallochemical group A ₂ K ⁰² B ₂² M ₂¹ (A = UO₂²⁺, K ⁰² = C₂O₂₋⁴, B ² = SO₄²⁻ or SeO₄²⁻, M ¹ = NCS⁻) of uranyl complexes. Uranium-containing chains are connected into a 3D framework via a system of electrostatic interactions with potassium or rubidium cations from outer spheres. Original Russian Text ? I.V. Medrish, E.V. Peresypkina, A.V. Virovets, L.B. Serezhkina, 2008, published in Kristallografiya, 2008, Vol. 53, No. 3, pp. 495–498.     

Crystal structure of britvinite [Pb7(OH)3F(BO3)2(CO3)][Mg4.5(OH)3(Si5O14)]: A new layered silicate with an original type of silicon-oxygen networks

The crystal structure of a new mineral britvinite Pb_7.1Mg_4.5(Si_4.8Al_0.2O₁₄)(BO₃)(CO₃)[(BO₃)_0.7(SiO₄)_0.3](OH, F)_6.7 from the Lángban iron-manganese skarn deposit (V?rmland, Sweden) is determined at T = 173 K using X-ray diffraction (Stoe IPDS diffractometer, λMoKα, graphite monochromator, 2θ_max = 58.43°, R = 0.052 for 6262 reflections). The main crystal data are as follows: a = 9.3409(8) ?, b = 9.3579(7) ?, c = 18.8333(14) ?, α = 80.365(6)°, β = 75.816(6)°, γ = 59.870(5)°, V = 1378.7(2) ?³, space group P1, Z = 2, and ρ_calcd = 5.42 g/cm³. The idealized structural formula of the mineral is represented as [Pb₇(OH)₃F(BO₃)₂(CO₃)][Mg_4.5(OH)₃(Si₅O₁₄)]. It is demonstrated that the mineral britvinite is a new representative of the group of mica-like layered silicates with structures in which three-layer (2: 1) “sandwiches” composed of tetrahedra and octahedra alternate with blocks of other compositions, such as oxide, oxide-carbonate, oxide-carbonate-sulfate, and other blocks. The tetrahedral networks (Si₅O₁₄)_∞∞ consisting of twelve-membered rings are fragments of the britvinite structure. Similar networks also form crystal structures of the mineral zeophyllite and the synthetic phase Rb₆Si₁₀O₂₃. In the crystal structures under consideration, the tetrahedral networks differ in the rotation of tetrahedra with respect to the layer plane. Original Russian Text ? O.V. Yakubovich, W. Massa, N.V. Chukanov, 2008, published in Kristallografiya, 2008, Vol. 53, No. 2, pp. 233–242.     

Phase equilibria in the Ba2Na3[B3O6]2F-BaF2 system

The phase equilibria in the Ba₂Na₃[B₃O₆]₂F-BaF₂ section, which belongs to the ternary mutual Ba, Na//BO₂,F system, have been studied by the methods of solid-phase synthesis, visual polythermal analysis, and differential-thermal analyses. It is shown that this section can be used to grow bulk Ba₂Na₃[B₃O₆]₂F crystals.     

Synthesis and structure of fullerene halides in the C60-(TiCl4 + Br2) system: Molecular structures of (C60Cl5)2, C60 X 6, C60 X 8, and C60 X 24( X = Cl, Br)

The reactions in the C₆₀-(TiCl₄ + Br₂) system have been performed in ampoules at elevated temperatures. The molecular structure of the fullerene halides (C₆₀Cl₅)₂, C₆₀ X ₆, C₆₀ X ₈, and C₆₀ X ₂₄ (X = Cl, Br) has been determined and refined using single-crystal X-ray diffraction. It has been established that an increase in the bromine concentration results in an increase in the number of halogen atoms attached to the fullerene cage and in an increase in the relative fraction of bromine atoms in mixed halogen derivatives from almost pure chlorides (C₆₀Cl₅)₂ and C₆₀Cl₆ to halides C₆₀ X ₈ and C₆₀ X ₂₄ with a high relative bromine content. Original Russian Text ? S.I. Troyanov, A.V. Burtsev, E. Kemnitz, 2009, published in Kristallografiya, 2009, Vol. 54, No. 2, pp. 268–275.     

Crystal structure of bis[diethylenetriamine-N′-(3-propionato)-N, N′,N″,O,O′]dicopper(II) Diperchlorate, [Cu2(4-Dtmp)2](ClO4)2

A complex of copper(II) with the diethylenetriaminemonopripionate ligand [Cu₂(4-Dtmp)₂](ClO₄)₂ (I) is synthesized and characterized using X-ray diffraction. The crystals of compound I are monoclinic, a = 7.740(2) Å, b = 19.199(3) Å, c = 8.449(2) Å, β = 91.61(2)°, Z = 2, and space group P2₁/n. The structural units of crystal I are centrosymmetric dimeric cations and statistically disordered ClO ₄ ⁻ anions. In the cation, the copper atom is coordinated by three N atoms [mean Cu-N, 2.01(1) Å] and two O atoms [Cu-O, 2.134(6) Å and 1.958(7) Å] of the pentadentate bridging-chelate Dtmp ligand, which occupy vertices of the trigonal bipyramid. The binuclear cations are linked via centrosymmetric pairs of hydrogen bonds into ribbons aligned parallel to the a axis of the crystal. The ClO ₄ ⁻ anions form columns in the same direction. In the crystal, the cationic ribbons and anionic columns alternate in a chessboard fashion. __________ Translated from Kristallografiya, Vol. 50, No. 3, 2005, pp. 450–454. Original Russian Text Copyright ? 2005 by Antsyshkina, Sadikov, Poznyak, Sergienko.     

The structure of Ag- and Li-borate glasses of the composition (Ag2O·2B2O3)1-x(AgI)x and (Li2O·2B2O3)

In both Li- and Ag-diborate glasses, the interpenetrating systems of diborate chains characteristics of the crystalline structure are completely destroyed. The Li-diborate glass is a disordered mixture of all possible borate-like configurations characterized by an ordering distance of about 4.5 Å for trigonal and of about 4 Å for tetrahedral borate units. In the Ag-diborate glass, the main features of the neutron scattering diagram can be simulated for small amounts of AgI (x = 0.1) by an ordering of diborate units (cages) at a separation of 6.7 Å. For a greater amount of AgI (x = 0.6), an appropriate number of diborate units have a separation of about 8.8 Å and the AgI phase forms clusters with a maximum diameter of about 8 Å.     

Solvothermal Syntheses and Crystal Structures of Neodymium Thiostannates [Nd(dien)3]2[(Sn2S6)Cl2] and [Nd(dien)3]2[(Sn2S6)(SH)2]

Abstract  

Two neodymium thiostannates [Nd(dien)₃]₂[(Sn₂S₆)Cl₂] (1) and [Nd(dien)₃]₂[(Sn₂S₆)(SH)₂] (2) (dien = diethylenetriamine) were synthesized by the reaction of tin and sulfur in the presence of NdCl₃ and Nd₂O₃, respectively under solvothermal conditions. Compounds 1 and 2 crystallize in monoclinic space group P2₁/n. Crystallographic data for 1: a = 11.6722(16), b = 15.119(2), c = 14.1566(19) ?, β = 96.213(3)°, V = 2483.6(6) ?³, Z = 4. For 2: a = 11.7190(14), b = 15.2168(19), c = 14.2209(18) ?, β = 95.775(4)°, V = 2523.1(5) ?³, Z = 4. The nine-coordinate [Nd(trien)₃]³⁺ complex cation formed in situ acts as the counter ion to the [Sn₂S₆]⁴⁻ anion. The [Nd(dien)₃]³⁺, [Sn₂S₆]⁴⁻ and Cl^– (or SH^–) ions form a 3-dimensional network structure through the N–H···S and N–H···Cl hydrogen bonds.     

Synthesis and Crystal Structure of Copper II and Silver I Complex with 1,4-diazabicyclo[2.2.2]octane[Cu(CBC)2(Dabco)(H2O)] n (1) and [Ag2(HBC)2(Dabco)] n (2)

Two 1D polymeric complex, [Cu(CBC)₂(Dabco)(H₂O)] _n (1) and [Ag₂(HBC)₂(Dabco)] _n (2) have been synthesized and characterized by X-ray single crystal analysis, where CBCH is p-chlorobenzoic acid, HBCH 2 is 2-hydroxybenzoic acid and Dabco is 1,4-diazabicyclo[2.2.2]octane. Complex 1 has been obtained in high yield by hydrothermal synthesis from CuO and CBCH and Dabco, and complex 2 has been obtain by evaporation of the solvent from silver salicylate and Dabco, 1 crystallizes in the orthorhombic space group Pmn2 ₁ with a = 24.3310(5) ?, b = 6.9050(6) ?, c = 5.9980(5) ?, Z = 2, V = 1007.70(4) ?³ and Dx = 1.657 g cm⁻³, 2 crystallizes in the monoclinic space group P2 ₁ /m with a = 10.292(3) ?, b = 6.913(2) ?, c = 14.417(4) ?, β = 95.660(5), Z = 2, V = 1020.8(5) ?³ and Dx = 1.959 g cm⁻³. The final R value is 0.0302 for 1323 measured reflections for 1 and the final R value is 0.0684 for 1545 measured reflections for 2. The atomic arrangement is built by infinite one-dimensional polymeric chain in both complexes. These chains are cross-linked by hydrogen bonds involving the coordinated water molecules to form a two-dimensional framework in complex 1.     

Magnetic behaviour of 20Fe2O380[3B2O3(1−χ)PbOχAs2O3] glasses

The results of magnetic measurements performed on 20Fe₂O₃80[3B₂O₃(1?χ)PbOχAs₂O₃] glasses, in the temperature range 4.2 to 300 K are reported. By decreasing the temperature a downward curvature of reciprocal susceptibility is observed for T<50 K. The composition dependence of the paramagnetic Curie temperatures and Curie constants is discussed.     

Synthesis and structure of (NH4)4[(DMF)2Mo8O26]· 2CH3CH2OH·2H2O (DMF= N , N -dimethylformamide)

A new organic-inorganic hybrid γ-octamolybdate complex, (NH₄)₄[(C₃H₇NO)₂Mo₈O₂₆]·2CH₃CH₂OH·2H₂O was synthesized from the mixture of ethanol, DMF, 4-aminobenzoic acid, (NH₄)₆Mo₇O₂₄·4H₂O, HCl and H₂O. The structure was determined by X-ray crystallography. It crystallizes in monoclinic P2₁/n space group with the crystal cell parameters of a = 8.8825(4), b = 21.1608(10), c = 11.1343(6) ?, β = 104.7720(10)°, V = 2023.64(17) ?³ and Z = 2. The crystal X-ray analysis shows that two DMF molecules are bound to γ-octamolybdate anion. The molecular structure is stabilized by the complex hydrogen bonding.     

Crystal structure of R[UO2(CH3COO)3] (R = NH 4+ , K+, or Cs+)

The single crystal structure of NH₄[UO₂(CH₃COO)₃] (I), K[UO₂(CH₃COO)₃] (II), and Cs[UO₂(CH₃COO)₃] (III) is studied by X-ray diffraction. I and II crystallize in the tetragonal crystal system. The crystal data are as follows: a = 13.6985(3) and c = 27.5678(14) ?, V = 5173.1(3) ?³, space group I4₁/a, Z = 16, and R = 0.023 for I; a = 13.8890(5) and c = 26.0839(18) ?, V = 5031.7(4) ?³, space group I4₁/a, Z = 16, and R = 0.037 for II. Crystals III are orthorhombic, a = 18.176(2), b = 13.119(2), and c = 22.088(4) ?, V = 5267(1)?³, space group Pbca, Z = 16, and R = 0.0424. In structures I–III, the uranium-containing structural units are represented by discrete mononuclear [UO₂(CH₃COO)₃]⁻ groups, which belong to the AB ₃⁰¹ (A = UO₂²⁺, B ⁰¹=CH₃COO⁻) crystal chemical group of uranyl complexes.     

Crystal structure of tetraphenylphosphonium 2-{[( Z )-Hydroxy(phenyl)methylene]ammonio}nonahydro- closo -Decaborate: The intramolecular O-H···B3 hydrogen bond in the [B10H9NHC(OH) Ph ]? anion

The compound (PPh ₄)[B₁₀H₉NHC(OH)Ph] is synthesized and its X-ray diffraction study is performed (120 K, R = 0.0875 for 5531 observed reflections). The NHC(OH)Ph substituent occupies the equatorial position in the polyhedral anion. The orientation of the substituent is stabilized by the intramolecular specific interaction of the OH group with the B atoms of the apical B(1)B(2)B(3) face, which can be considered as a multicenter hydrogen bond (the O···B distances are 3.001, 2.877, and 3.251 ?; the H···B distances are 2.00, 2.18, and 2.30 ?; and the O-H···B angles are 156°, 121°, and 148°). Original Russian Text ? I.N. Polyakova, K.Yu. Zhizhin, N.T. Kuznetsov, 2007, published in Kristallografiya, 2007, Vol. 52, No. 2, pp. 287–289.     

Crystal structure of the Lanthanum(III) complex [La(DMSO)6(H2O)PW12O40] · C2H5OH (DMSO is dimethyl sulfoxide)

The crystal structure of the [La(DMSO)₆(H₂O)PW₁₂O₄₀] · C₂H₅OH complex (I) (where DMSO is dimethyl sulfoxide) is determined by X-ray diffraction analysis. The coordination polyhedron of the La atom is a distorted tricapped trigonal prism in which two cap sites are occupied by oxygen atoms of the heteropolyanions. For these atoms, the La-O distances [2.760(9) and 2.801(9) Å] are considerably longer than the other distances [ranging from 2.441(10) to 2.569(10) Å] in the environment of the La atom. __________ Translated from Kristallografiya, Vol. 47, No. 6, 2002, pp. 1039–1041. Original Russian Text Copyright ? 2002 by Grigoriev, Shirokova, Fedoseev, Den Auwer.     

Pincer ligand coordination at Co3 and Ru6 clusters: Syntheses, reactivity studies, and X-ray diffraction structures of [PhCCo3(CO)8]2(dppx) and [Ru6(μ6-C)(CO)16]2(dppx)

The reaction of the pincer diphosphine ligand 4,6-bis(diphenylphosphinomethyl)-m-xylene (dppx) with the metal cluster compounds PhCCo₃(CO)₉ and Ru₆(μ₆-C)(CO)₁₇ has been explored. Both clusters react with dppx to afford the simple substitution products [PhCCo₃(CO)₈]₂(dppx) and [Ru₆(μ₆-C)(CO)₁₆]₂(dppx), where two cluster units are tethered by the pincer ligand. The molecular structures of the title products and the 2:1 cluster-pincer ligand stoichiometry have been established by X-ray crystallography. The stability of [PhCCo₃(CO)₈]₂(dppx) and [Ru₆(μ₆-C)(CO)₁₆]₂(dppx) has been investigated under gentle thermolysis conditions (ca. 55–65°C). Both dppx-substituted clusters are unstable with [PhCCo₃(CO)₈]₂(dppx) decomposing and [Ru₆(μ₆-C)(CO)₁₆]₂(dppx) transforming into the diphosphine-bridged cluster Ru₆(μ₆-C)(CO)₁₅(μ-dppx) as the major observable product. The identity of the latter cluster has been ascertained by IR and NMR spectroscopies and mass spectrometry.     

Variation of optical basicity with probe ion,for Cs2O + B2O3 and Li2O + B2O3 glasses

Optical basicities (Γ) for Cs₂O + B₂O₃ and Li₂O + B₂O₃ glasses have been measured as a function of glass composition, using Tl⁺, Pb²⁺ and Bi³⁺ probe ions. The three probe ions register different values of Γ for glasses of given composition (and also for pure B₂O₃ glass and water). The divergence decreases as the alkali metal ion size decreases.For the Li₂O + B₂O₃ glasses, ideal (calculated) optical basicities agree within experimental precision with experimental values registered by Pb²⁺ (Γ_Pb²⁺) up to about 15 mol% Li₂O. For higher Li₂O contents, and for the Cs₂O + B₂O₃ glasses, ideal optical basicities agree less well with Γ_Pb²⁺, but show similar trends with composition to those shown by Γ_Pb²⁺.     

Synthesis, Crystal Structure and Properties of the Binuclear Complex [Sm2(C10H9N2O4)2(C10H8N2O4)2(H2O)4]

Abstract  A novel binuclear Smarium (III) complex with N-(2-propionic acid)-salicyloyl hydrazone (C₁₀H₁₀N₂O₄, H₃L) was prepared and characterized. The crystal structure of [Sm₂(H₂L)₂(HL)₂(H₂O)₄] (1) was determined by X-ray single crystal diffractometry. 1 crystallizes in the monoclinic systerm, space group P2(1)/c, with a = 0.10229(2), c = 31.549(7), b = 0.70599(15) nm, and Z = 4. In the structure, Sm(III) is nine-coordinated by carboxyl O and acyl O atoms and imido N atoms of two ligands (H₂L and HL forms) and O atoms from two water molecules. H₂L and HL act as tridentate ligands which form two stable five-numbered chelating rings sharing one edge in the keto form for each ligand, and the carboxyl groups of two ligands were coordinated via bidentated bridging form. The coordination polyhedron around Sm (III) was described as a monocapped square antiprism. The inter- and intramolecular hydrogen bonds resulted in a three-dimensional network and provided extra stability for the structure. The complex was researched the interaction with calf thymus DNA by electronic absorption titration and emission titration. The results show that the complex is bound to calf thymus DNA mainly by intercalation .The complex also shows good fluorescence property. Index Abstract  The title compound, [Sm₂(H₂L)₂(HL)₂(H₂O)₄] was synthesized by the treatment of N-(2-propionic acid)-salicyloyl hydrazone (C₁₀H₁₀N₂O₄, H₃L) and Sm(NO₃) · 4H₂O and its crystal structure determined. Single crystal X-ray diffraction analysis reveals that Sm (III) is nine-coordinated by carboxyl O and acyl O atoms and imido N atoms of two ligands (H₂L and HL forms) and O atoms from two water molecules. The carboxyl groups of two ligands were coordinated via bidentated bridging form. The coordination polyhedron around Sm (III) was described as a monocapped square antiprism. The inter- and intramolecular hydrogen bonds resulted in a three-dimensional network and provided extra stability for the structure.