Quantum dynamics of dissociative adsorption of H_2 and D_2:The time-dependent wave packet method

Ｒｅｃｅｎｔｐｒｏｇｒｅｓｓｉｎｓｕｒｆａｃｅｓｐｅｃｔｒｏｓｃｏｐｙａｎｄｍｏｌｅｃｕｌａｒｂｅａｍｓｃａｔｔｅｒｉｎｇａｎｄｄｅｔｅｃｔｉｏｎｔｅｃｈｎｉｑｕｅｓｍａｋｅｓｉｔｎｏｗｐｏｓｓｉｂｌｅａｔｔｈｅｍｉｃｒｏｓｃｏｐｉｃｌｅｖｅｌｔｏａｃｃｕｒａｔｅｌｙｍｅａｓｕｒｅｓｕｃｈｔｈｉｎｇｓａｓｄｉｓｓｏｃｉａｔｉｏｎｒａｔｅｓ,ａｄｓｏｒｂａｔｅｂｉｎｄｉｎｇａｎｄｇｅｏｍｅｔｒｙ,ａｎｄｍｏｂｉｌｉｔｉｅｓｏｆａｄｓｏｒｂｅｄｓｐｅｃｉｅｓｏｎｓｕｒｆａｃｅｓ.Ｔｈｉｓｋｉｎｄｏｆｅ…     

Structure and aggregation behavior of cobalt-di(2-ethylhexy1)-phosphoric acid complexes in solvent extraction systems

Ｔｈｅｓｏｌｖｅｎｔｅｘｔｒａｃｔｉｏｎｏｆｃｏｂａｌｔｗｉｔｈｏｒｇａｎｏｐｈｏｓｐｈｏｒｕｓａｃｉｄｉｃｅｘｔｒａｃｔａｎｔｓｉｓｃｈａｒａｃｔｅｒｉｚｅｄｂｙｉｔｓｈｉｇｈｅｒｅｘｔｒａｃｔｉｏｎｓｅｌｅｃｔｉｖｉｔｙｔｈａｎｎｉｃｋｅｌｆｒｏｍａｑｕｅｏｕｓｓｏｌｕｔｉｏｎｓ[1].Ｔｈｅｅｘｔｒａｃｔａｂｉｌｉｔｙａｎｄｓｅｌｅｃｔｉｖｉｔｙｏｆｍｅｔａｌｉｏｎｓａｒｅｃｌｏｓｅｌｙｒｅｌａｔｅｄｔｏｔｈｅｃｏｏｒｄｉｎａｔｉｏｎｓｔｒｕｃｔｕｒｅｏｆｍｅｔａｌｓｗｉｔｈｅｘｔｒａｃｔａｎ…     

Synthesis of a Novel Perfluorinated Vinyl Ether Containing Sulfonimide and Phosphonic Acid Functionalities

ＩｎｔｒｏｄｕｃｔｉｏｎＩｎｔｈｅｐａｓｔｄｅｃａｄｅｓ ,ｃｏｎｓｉｄｅｒａｂｌｅｒｅｓｅａｒｃｈｗｏｒｋｈａｓｂｅｅｎｆｏｃｕｓｅｄｏｎｔｈｅｆｌｕｏｒｉｎａｔｅｄｉｏｎｏｍｅｒｓ1 4 ｗｈｉｃｈｈａｖｅｅｘｃｅｐｔｉｏｎａｌｔｈｅｒｍａｌａｎｄｃｈｅｍｉｃａｌｓｔａｂｉｌｉｔｉｅｓ .5Ｔｈｅｒｅｆｏｒｅｔｈｅｙｈａｖｅｓｈｏｗｎｓｐｅｃｉａｌａｐｐｌｉｃａｔｉｏｎｓ ,ｓｕｃｈａｓｍｅｍｂｒａｎｅｓｅｐａｒａｔｉｏｎｉｎｔｈｅｅｌｅｃｔｒｏｃｈｅｍｉｃａｌｐｒｏｃｅｓｓｅｓａｎｄｓｕｐｅｒａｃｉ…     

Synthesis, Structure and Noncovalent Interactions of Palladium(II) Complexes with N-Benzoyl-β-phenylalaninate Dianion and Aromatic Diimine

Ｉｎｔｒｏｄｕｃｔｉｏｎ　　Ｎｏｎ ｃｏｖａｌｅｎｔｉｎｔｅｒａｃｔｉｏｎｓｈａｖｅａｂｉｇｉｎｆｌｕｅｎｃｅｏｎｔｈｅｃｏｎｆｏｒｍａｔｉｏｎａｌｏｒｇａｎｉｚａｔｉｏｎｏｆｔｈｅｂｉｏｍｏｌｅｃｕｌｅｓｗｈｉｃｈｉｓｒｅｓｐｏｎｓｉｂｌｅｆｏｒｔｈｅｒｅｇｉｏ ａｎｄｓｔｅｒｅｏ ｓｐｅｃｉｆｉｃｉｔｙｏｆｖａｒｉｏｕｓｂｉｏｌｏｇｉｃａｌｐｒｏｃｅｓｓｅｓ .1Ａｍｏｎｇｔｈｅｓｅｉｎｔｅｒａｃｔｉｏｎｓ ,ｔｈｅｉｎ ｔｒａｍｏｌｅｃｕｌａｒｓｔａｃｋｉｎｇｉｎｔｅｒａｃｔｉｏｎｂｅｔｗｅｅｎｓ…     

Mechanisms of Cytochrome C Extraction by Reverse Micelles

Ｔｈｅｒｅｖｅｒｓｅｍｉｃｅｌｌｅｓａｒｅｗａｔｅｒ ｉｎ ｏｉｌｍｉｃｒｏｅｍｕｌｓｉｏｎｄｒｏｐｌｅｔｓｓｔａｂｉｌｉｚｅｄｂｙａｓｕｒｆａｃｔａｎｔｉｎａｎｏｒｇａｎｉｃｓｏｌｖｅｎｔ .Ｔｈｅｐｏｌａｒｓｕｒｆａｃｔａｎｔｈｅａｄｇｒｏｕｐｓｓｕｒｒｏｕｎｄｓｍａｌｌｗａｔｅｒｐｏｏｌｓｗｉｔｈｉｎｗｈｉｃｈｈｙｄｒｏｐｈｉｌｉｃｍｏｌｅｃｕｌｅｓ,ｓｕｃｈａｓａｍｉｎｏａｃｉｄｓａｎｄｐｒｏｔｅｉｎｓ ,ｃａｎｂｅｓｏｌｕｂｉｌｉｚｅｄ .Ｔｈｅａｐｏｌａｒｓｕｒｆａｃ ｔａｎｔｈｙｄｒｏｃａｒ…     

Relationship between the helical structure and optical activity of some chiral cyclic esters

Ｈｅｌｉｃａｌｓｔｒｕｃｔｕｒｅ,ａｎｉｍｐｏｒｔａｎｔｆａｃｔｏｒａｆｆｅｃｔｉｎｇｔｈｅｏｐｔｉｃａｌａｃｔｉｖｉｔｙｏｆｃｈｉｒａｌｍｏｌｅｃｕｌｅｓ,ｈａｓｌｏｎｇｂｅｅｎｃｏｎｃｅｒｎｅｄｂｙｃｈｅｍｉｓｔｓａｎｄｐｈｙｓｉｃｉｓｔｓ.Ｉｎ1860,Ｐａｓｔｅｕｒｉｎｈｉｓｆａｍｏｕｓｓｔｕｄｙｏｎｔａｒｔａｒｉｃａｃｉｄｓａｓｋｅｄｔｈｅｑｕｅｓｔｉｏｎｗｈｅｔｈｅｒｔｈｅｏｐｔｉｃａｌａｃｔｉｖｉｔｙｉｓｄｕｅｔｏｔｈｅａｔｏｍｓｏｆｔｈｅｄｅｘｔｒｏａｃｉｄｇｒｏｕｐｅｄｏｎｔｈｅｓｐｉ…     

Structures that should be Described in Higher-Symmetry, Centrosymmetric Space Groups. Part 2. The Structures of [Ni(C_5H_4NO-2-CH=N-CH_2CH_2-N=CH-2-C_5H_4NO)(H_2O)_2]- (ClO_4)_2, {Ni[C_5H_4NO-2-CH=N-CH(CH_3)CH_2-N=CH-2- C_5H_4NO](H_2O)_2}

1　ＩＮＴＲＯＤＵＣＴＩＯＮＳｅｖｅｒａｌｉｎｃｏｒｒｅｃｔｓｐａｃｅｇｒｏｕｐｓｈａｖｅｂｅｅｎｒｅ ａｓｓｉｇｎｅｄｂｙｍａｋｉｎｇｕｓｅｏｆｓｉｍｕｌａｔｅｄｓｔｒｕｃｔｕｒｅｆａｃｔｏｒｓ;ｈｏｗｅｖｅｒ,ｔｈｅｃｒｕｘｏｆｔｈｉｓｏｒａｎｙｓｐａｃｅｇｒｏｕｐｒｅｖｉｓｉｏｎｉｓｔｈｅａｃｃｕｒａｔｅｒｅｐｏｒｔｉｎｇｏｆｔｈｅｓｐａｃｅｇｒｏｕｐａｎｄａｔｏｍｉｃｃｏｏｒｄｉｎａｔｅｓｏｆｔｈｅｉｎｃｏｒｒｅｃｔｌｙｄｅｔｅｒｍｉｎｅｄｓｔｒｕｃｔｕｒｅｓｉｎｃｅｔｈｅｔｒｕｅｓｔｒｕｃ…     

Synthesis and Crystal Structure of a Novel Hydrogen-Bonded Three-Dimensional Polymer [Zn(1,4-benzenedicarboxylate)-(pyridine)·H_2O]_n

ＩｎｔｒｏｄｕｃｔｉｏｎＤｅｓｉｇｎａｎｄｓｙｎｔｈｅｓｅｓｏｆｎｏｖｅｌｓｕｐｒａｍｏｌｅｃｕｌａｒｃｏｍ ｐｌｅｘｅｓｗｉｔｈｕｎｕｓｕａｌａｎｄｔａｉｌｏｒａｂｌｅｓｔｒｕｃｔｕｒｅｓａｒｅｆｕｎｄａ ｍｅｎｔａｌｓｔｅｐｓｉｎｄｉｓｃｏｖｅｒｙａｎｄｆａｂｒｉｃａｔｉｏｎｏｆｖａｒｉｏｕｓｔｅｃｈ ｎｏｌｏｇｉｃａｌｌｙｕｓｅｆｕｌｆｕｎｃｔｉｏｎａｌｓｕｐｒａｍｏｌｅｃｕｌａｒｄｅｖｉｃｅｓ .1 3Ｒｅｃｅｎｔｌｙ ,ｃｏｎｓｉｄｅｒａｂｌｅｅｆｆｏｒｔｓｈａｖｅｂｅｅｎｄｅｖｏｔｅｄｔｏｃｒ…     

Synthesis, Crystal Structure and Reactivity of (2,4-C_7H_(11) )_2Yb·DME

ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｏｒｇａｎｏｍｅｔａｌｌｉｃｃｈｅｍｉｓｔｒｙｏｆｌａｎｔｈａｎｉｄｅｍｅｔａｌｓｉｎｌｏｗｏｘｉｄａｔｉｏｎｓｔａｔｅｓｉｓｃｕｒｒｅｎｔｌｙｕｎ ｄｅｒｇｏｉｎｇａｒａｐｉｄｄｅｖｅｌｏｐｍｅｎｔ.Ｔｈｅｓｔｕｄｉｅｓｏｎｄｉｖａｌｅｎｔｍｅｔａｌ ｃｏｍｐｌｅｘｃｈｅｍｉｓｔｒｙｈａｖｅｌｅｄｔｏａｖａｒｉｅｔｙｏｆｎｅｗｃｌａｓｓｅｓｏｆｃｏｍｐｌｅｘｅｓａｎｄｒｅａｃｔｉｖｉｔｙｐａｔｔｅｒｎｓ[14 ] .Ｔｈｅｉｍｐｏｒｔａｎｃｅｏｆｓｔｅｒｉｃｆａｃｔｏｒｓｃ…     

Synthesis and Characterization of Surfactant-encapsulated Polyoxoanions: [(C_nH_(2n+1))_2N(CH_3)_2]_(12)[Mo_(36)(NO)_4O_(108)(H)2O)_(16)] (n=12, 18)

ＩｎｔｒｏｄｕｃｔｉｏｎＳｕｐｒａｍｏｌｅｃｕｌａｒｓｅｌｆ ｏｒｇａｎｉｚａｔｉｏｎａｓａｃｏｎｔｒｏｌｌａｂｌｅｔｅｃｈｎｉｑｕｅｆｏｒｔｈｅａｒｔｉｆｉｃｉａｌｓｕｐｒａｍｏｌｅｃｕｌａｒａｒｃｈｉｔｅｃｔｕｒｅａｔｍｏｌｅｃｕｌａｒａｎｄ/ｏｒｎａｎｏｓｉｚｅｄｌｅｖｅｌｉｓｓｈｏｗｉｎｇｆａｓｃｉｎａｔｉｎｇｐｅｒｓｐｅｃｔｉｖｅｓｉｎｔｈｅｆｉｅｌｄｏｆｔｈｅｍｏｌｅｃｕｌａｒｍａｔｅｒｉａｌｓｄｅ ｓｉｇｎ ,ｄｕｅｔｏｔｈａｔｏｒｇａｎｉｃａｎｄｉｎｏｒｇａｎｉｃｃｏｍｐｏｎｅｎｔｓ…     

Synthesis,spectral, catalytic,and thermal studies of vanadium complexes with quadridentate schiff bases

The paper reports the synthesis and characterization of vanadium complexes of N,N′-(±)-trans-bis(2,4-dihydroxyacetophenone)-1,2-cyclohexanediamine (H₂L¹) and N,N′-(±)-trans-bis(2,4-dihyroxy-5-nitroacetophenone)-1,2-chyclohexanediamine (H₂L²). All the complexes were characterized by elemental analysis, magnetic susceptibility measurements, infrared and electronic spectra, and thermogravimetric analysis. The X-ray patterns of the [VO(L¹)] · H₂O (I) and [VO(L²)] · H₂O (II) complexes show the monoclinic system with the unit cell parameters a = 26.1352, b = 11.7149, c = 6.0401 β = 115.38° and a = 29.3787, b = 12.9398, c = 5.9175 β = 96.84°, respectively. The complexes I and II catalyze the oxidation of styrene in the presence of hydrogen peroxide.     

Mono‐ and Dimethyl‐1,2,4‐Triazolate as Ligands for the Mercuric Ion in the Cationic Three‐dimensional Coordination Polymer of [Hg2(Mmt)(Dmt)2](NO3)(H2O)

Colourless crystals of [Hg₂(Mmt)(Dmt)₂](NO₃)(H₂O) were obtained from a reaction of mercuric nitrate with monomethyl‐ and dimethyl‐1,2,4‐triazolate (Mmt^? and Dmt^?, respectively). In the crystal structure (monoclinic, C2/c (no. 15), a = 2579.4(4), b = 1231.1(2), c = 1634.8(2) pm, β = 128.32(1)°, V = 4073.3(11)·10⁶·pm³, Z = 8, R₁ [I₀ > 2σ(I₀)]: 0.0355), half of the mercuric ions are essentially two‐coordinate (Hg–N: 210‐215 pm), the other half are tetrahedrally surrounded by N‐donor atoms (Hg–N: 221, 225 pm) of the Mmt^? and Dmt^? anions. These three‐N ligands construct a three‐dimensional framework.     

Syntheses and structural determinations of the nine-coordinate rare earth metal: Na4[DyIII(dtpa)(H2O)]2·16H2O,Na[DyIII(edta)(H2O)3]·3.25H2O and Na3[DyIII(nta)2(H2O)]·5.5H2O

Three complexes, Na₄[Dy^III(dtpa)(H₂O)]₂?·?16H₂O, Na[Dy^III(edta)(H₂O)₃]?·?3.25H₂O and Na₃[Dy^III (nta)₂(H₂O)]?·?5.5H₂O, have been synthesized in aqueous solution and characterized by FT–IR, elemental analyses, TG–DTA and single-crystal X-ray diffraction. Na₄[Dy^III(dtpa)(H₂O)]₂?·?16H₂O crystallizes in the monoclinic system with P2₁/n space group, a?=?18.158(10)?Å, b?=?14.968(9)?Å, c?=?20.769(12)?Å, β?=?108.552(9)°, V?=?5351(5)?ų, Z?=?4, M?=?1517.87?g?mol^?1, D _c?=?1.879?g?cm^?3, μ?=?2.914?mm^?1, F(000)?=?3032, and its structure is refined to R ₁(F)?=?0.0500 for 9384 observed reflections [I?>?2σ(I)]. Na[Dy^III(edta)(H₂O)₃]?·?3.25H₂O crystallizes in the orthorhombic system with Fdd2 space group, a?=?19.338(7)?Å, b?=?35.378(13)?Å, c?=?12.137(5)?Å, β?=?90°, V?=?8303(5)?ų, Z?=?16, M?=?586.31?g?mol^?1, D _c?=?1.876?g?cm^?3, μ?=?3.690?mm^?1, F(000)?=?4632, and its structure is refined to R ₁(F)?=?0.0307 for 4027 observed reflections [I?>?2σ(I)]. Na₃[Dy^III(nta)₂(H₂O)]?·?5.5H₂O crystallizes in the orthorhombic system with Pccn space group, a?=?15.964(12)?Å, b?=?19.665(15)?Å, c?=?14.552(11)?Å, β?=?90°, V?=?4568(6)?ų, Z?=?8, M?=?724.81?g?mol^?1, D _c?=?2.102?g?cm^?3, μ?=?3.422?mm^?1, F(000)?=?2848, and its structure is refined to R ₁(F)?=?0.0449 for 4033 observed reflections [I?>?2?σ(I)]. The coordination polyhedra are tricapped trigonal prism for Na₄[Dy^III(dtpa)(H₂O)]₂?·?16H₂O and Na₃[Dy^III(nta)₂(H₂O)]?·?5.5H₂O, but monocapped square antiprism for Na[Dy^III(edta)(H₂O)₃]?·?3.25H₂O. The crystal structures of these three complexes are completely different from one another. The three-dimensional geometries of three polymers are 3-D layer-shaped structure for Na₄[Dy^III(dtpa)(H₂O)]₂?·?16H₂O, 1-D zigzag type structure for Na[Dy^III(edta)(H₂O)₃]?·?3.25H₂O and a 2-D parallelogram for Na₃[Dy^III(nta)₂(H₂O)]?·?5.5H₂O. According to thermal analyses, the collapsing temperatures are 356°C for Na₄[Dy^III(dtpa)(H₂O)]₂?·?16H₂O, 371°C for Na[Dy^III(edta)(H₂O)₃]?·?3.25H₂O and 387°C for Na₃[Dy^III(nta)₂(H₂O)]?·?5.5H₂O, which indicates that their crystal structures are very stable.     

Synthesis and structure of a polymeric ten-coordinate rare earth metal complex with nta ligand: {[EuIII(C-nta)(T-nta)]·3H2O} n with a novel cage-like 3-D structure

The polymeric ten-coordinate rare earth metal (RE) complex with nta, {[Eu^III(C-nta)(T-nta)] · 3H₂O} _n , has been synthesized in aqueous solution and characterized by FT-IR, elemental analyses, TG-DTA and single-crystal X-ray diffraction technique. The {[Eu^III(C-nta)(T-nta)] · 3H₂O} _n crystallizes in the cubic system with P2₁3 space group, a = b = c = 12.4153(3) Å, V = 1913.69(8) ų, Z = 4, M = 582.24 g mol^?1, D _c = 2.021 Mg m^?3, μ = 3.360 mm^?1, F(000) = 1148, and its structure is refined to R ₁(F) = 0.0204 for 1277 observed reflections [I ≥ 2.0σ(I)]. The coordination polyhedron adopts distorted C_3v mono-top-capped & tri-lateral-capped trigonal prismatic conformation (MT&TL-TP); the three-dimensional geometry is a cage-like 3-D structure. According to thermal analyses, the collapsing temperature of the crystal structure is 173°C, indicating that its crystal structure is very stable.     

Synthesis,Characterization and Nuclease Activity of Ternary Copper(Ⅱ) Complexes Containing Dipyrido[3,2-a:2',3'-c]phenazine and L-α-Amino Acids

Two new complexes: [Cu(dppz)(L‐val)(H₂O)]ClO₄ ( 1 ) and [Cu(dppz)(L‐tyr)(H₂O)]ClO₄·1.5H₂O ( 2 ) (dppz=dipyrido[3,2‐a:2′,3′‐c]phenazine, L‐val=L‐valinate, L‐tyr=L‐tyrosinate) have been synthesized and investigated by elemental analysis, molar conductivity, UV‐Vis and IR spectroscopies. Complex 1 has been structurally characterized by the single‐crystal X‐ray diffraction method, which crystallizes in the triclinic space group P‐1 in a unit cell of a=0.9095(2) nm, b=1.3301(3) nm, c=1.3552(3) nm, α =93.518(3) °, β=97.192(3) °, γ=106.361(3) °, V=1.5526(6) nm³, Z=2, D_c=1.598 g·cm^?3, µ=0.849 mm^?1. The DNA binding and cleavage properties of the complexes have been studied by UV spectroscopy, fluorescence spectroscopy, viscosity measurement and agarose gel electrophoresis. The results show that the complexes can bind DNA by intercalation and cleave pBR322 DNA by free hydroxyl radical induced by the complexes in the presence of ascorbate, giving the order of the binding abilities and cleavage activity of the complexes to DNA: complex 2 > 1 .     

Crystal Structure of Tetrakis (phenacetin) Dihydrogentetraiodide Dihydrate {[H5C2OC6H4N (H)C(CH3)O]4·H2I4·2H2O}

(Phenacetin)₄·₂I₄·2H₂O is triclinic, a = 13.641 (7), b = 12.807 (6), c = 7.201 (3) Å, α = 99.8 (4), b? = 86.5 (4), γ = 104.0 (5)°, P1 , Z = 1. The ordered crystal structure has been refined to R_F = 0.050, using 4173 independent reflections measured on a four-circle diffractometer with MoKa (graphite monochromator) radiation. The crystals are composed of alternating positively and negatively charged slices; each positive slice contains a double layer of stacks of hemi-protonated phenacetin molecules which are H-bonded through their carbonyl groups (d(O - - - O) = 2.432 (4) Å) while each negative slice contains a single layer of I^2?₄-ions linked in chains along [100] through H-bonds to pairs of water molecules. The axes of the phenacetin stacks are parallel to the planes of the (I^2?₄·2H₂O)-layers. The I^2?₄-ion is centro-symmetric and can be approximately represented as I^?- - - I–I- - - I^? (d(I^? - - - I) = 3.404 (1) Å; d(I–I) = 2.774 (1) Å). The compound is a pseudo-type A basic salt.     

ANIONIC COORDINATION COMPLEXES OF Mo AND W WHICH CRYSTALLIZE FROM LIQUID CLATHRATE MEDIA WITH OXONIUM ION-CROWN ETHER CATIONS

Abstract

The complexes [H₃O⁺·18-crown-6][MoOCl₄(H₂O)^?], 1, and [H₂O·aza-18-crown-6·(H⁺)] [MoOCl₄(H₂O)^?], 3, were synthesized from a mixture of Mo(CO)₆, HCl(g), H₂O and either 18-crown-6 for 1 or mono-aza-18-crown-6 for 3, in toluene. For complex 4, [H₂O·aza-18-crown-6·(H⁺)]₂[WOCl₄(H₂O)^?][Cl^?], reaction conditions were as for 3 except W(CO)₆ was used in place of Mo(CO)₆. Similarly, for complex 2, [H₃O⁺·18-crown-6][WOBr₄(H₂O)^?], W(CO)₆ and HBr were used in the reaction mixture. These reactions were promoted by UV radiation and formed liquid clathrates almost immediately upon reaction. X-ray crystal structures were performed on each compound. Complex 1 crystallizes in the triclinic space group P/i with a = 10.206(1), b = 10.486(1), c = 11.701(1) Å, α = 71.11(1), β = 74.60(1), γ = 75.08(1)°, and D _c = 1.649 g cm^?3 for Z = 2. Refinement based on 3925 observed reflections led to a final R value of 0.078. Complex 2 crystallizes in the monoclinic space group P2₁/c with a = 9.710(1), b = 19.824(1), c = 12.399(1) Å, β = 104.58(1)°, and D _c = 2.369 g cm^?3 for Z = 4. Refinement based on 2008 observed reflections led to a final R value of 0.090. Complex 3 crystallizes in the orthorhombic space group Pnmn with a = 16.927(1), b = 12.226(1), c = 11.167(1) Å, and D _c = 1.598 g cm^?3 for Z = 4. Refinement based on 1486 observed reflections led to a final R value of 0.040. Complex 4 crystallizes in the monoclinic space group C2/m with a = 11.761(2), b = 12.096(2), c = 14.966(1) Å, β = 132.91(1)°, and D _c = 1.502 g cm^?3 for Z = 4. Refinement based on 2021 observed reflections led to a final R value of 0.051. In all cases the metal coordination sphere was essentially octahedral with the water ligand trans to the oxo species.     

Syntheses and structures of nine-coordinate K3[DyIII(nta)2(H2O)]·5H2O and eight-coordinate (NH4)3[DyIII(nta)2] complexes

K₃[Dy^III(nta)₂(H₂O)]·5H₂O and (NH₄)₃[Dy^III(nta)₂] have been synthesized in aqueous solution and characterized by IR, elemental analysis and single-crystal X-ray diffraction techniques. In K₃[Dy^III(nta)₂(H₂O)]·5H₂O the Dy^III ion is nine coordinated yielding a tricapped trigonal prismatic conformation, and its crystal belongs to monoclinic system and C2/c space group. The crystal data are as follows: a = 15.373(5) Å, b = 12.896(4) Å, c = 26.202(9) Å; β = 96.122(5)°, V = 5165(3) ų, Z = 8, D _c = 1.965 g·cm^?3, μ = 3.458 mm^?1, F(000) = 3016, R ₁ = 0.0452 and wR ₂ = 0.1025 for 4550 observed reflections with I ≥ 2σ(I). In (NH₄)₃[Dy^III(nta)₂] the Dy^III ion is eight coordinated yielding a usual dicapped trigonal anti-prismatic conformation, and its crystal belongs to monoclinic system and C2/c space group. The crystal data are as follows: a = 13.736(3) Å, b = 7.9389(16) Å, c = 18.781(4) Å; β = 104.099(3)°, V = 1986.3(7) ų, Z = 2, D _c = 1.983 g·cm^?3, μ = 3.834 mm^?1, F(000) = 1172, R ₁ = 0.0208 and wR ₂ = 0.0500 for 2022 observed reflections with I ≥ 2σ(I). The results indicate that the difference in counter ion also influences coordination numbers and structures of rare earth metal complexes with aminopolycarboxylic acid ligands.     

Mononuclear eight-coordinate (NH4)3[YIII(Nta)2] and one-dimensional unlimited zigzag type nine-coordinate {K[YIII(Egta) · 4H2O}n complexes: Syntheses and structural determination

The title complexes (NH₄)₃[Y^III(Nta)₂] (I) (H₃Nta = nitrilotriacetic acid) and {K[Y^III(Egta)] · 4H₂O} _n (II) (H₄Egta = ethyleneglycol-bis-(2-aminoethylether)-N,N,N′,N′-tetraacetic acid) were prepared, and their molecular and crystal structures were determined by single-crystal X-ray diffraction techniques. Complex I crystallizes in the rhombohedral crystal system with R $ \bar 3 $ \bar 3 c space group. The central Y³⁺ ion is eight-coordinated by two nitrogen and six oxygen atoms, which come from two tetradentate Nta ligands. The crystal data are as follows: a = 7.9340(14) ?, c = 54.611(15) ?, V = 2977.1(11) ?³, Z = 6, ρ_calcd = 1.738 mg/cm³, μ = 3.011 mm⁻¹, F(000) = 1596, R = 0.0234 and wR = 0.0641 for 686 observed reflections with I ≥ 2σ(I). The {K[Y^III(Egta)] · 4H₂O} _n is nine-coordinated by two nitrogen and seven oxygen atoms and produces a 1D unlimited zigzag-type chain through a bridging carboxylic group. {K[Y^III(Egta)] · 4H₂O} _n crystallizes in the monoclinic crystal system with C2/c space group. The crystal data are as follows: a = 37.588(5) ?, b = 13.7101(19) ?, c = 8.6070(12) ?, β = 99.929(2)°, V = 4369.0(11) ?³, Z = 8, ρ_calcd = 1.753 mg/cm³, μ = 2.934 mm⁻¹, F(000) = 2368, R = 0.0385 and wR = 0.0800 for 4082 observed reflections with I ≥ 2σ(I).     

THE PHENOMENON OF CONGLOMERATE CRYSTALLIZATION. PART 53. THE CRYSTALLIZATION BEHAVIOR OF TWO COBALT(III) CARBONATO AMINE COMPOUNDS

Abstract

Two new cobalt(III) carbonato amine compounds were synthesized, and their crystal structures were determined.

Compound (I), Na₂[Co(tren)(CO₃)]₂(CIO₄)₄·3H₂O, Co₂C₁₄CI₄H₄₂N₈Na₂O 25, crystallized as a racemate in the orthorhombic system, space group Pcab (No. 61). The cell dimensions, obtained from the centering of 25 reflections, are a = 10.684(5)å, b = 18.559(8)å, c = 37.528(10)å, V= 7441(5)å³. FW= 1028.18, Z= 8, F(000) = 4203.87, dc = 1.836 Mg·m^?3, μ = 1.30 mm^?3, λ = 0.70930å. A total of 3457 data were collected over the range of 4° ≤2θ ≤40°; of these, 2377 (independent and I≥2.5σ(I)) were used in the structural analysis. The final RF and Rw residuals were 0.055 and 0.064.

Compound (II), [cis-β-Co(trien)(CO₃)](HCO₃)· H₂O, CoC₈H₂₁N₄O₇, crystallized as a conglomerate in the orthorhombic system, space group P2₁2₁2₁ (No. 19). The cell dimensions, obtained from the centering of 25 reflections, are a = 8.869(4)å, b = 12.032(8)å, c = 12.522(7)å, V = 1336(1)å³. FW = 344.20, Z = 4, F(000) = 713.62, dc = 1.701 Mg·m^?3, μ = 1.32mm^?1, λ = 0.70930å. A total of 3504 data were collected over the range of 4° ≤2θ ≤40°; of these, 2497 (independent and I≥ 2.5σ(I)) were used in the structural analysis. The final RF and Rw residuals were 0.049 and 0.059.