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.     

Dimeric ensembles in the crystal structures of mixed-ligand coordination compounds ML(<Emphasis Type="Italic">i</Emphasis>-Bu<Subscript>2</Subscript>PS<Subscript>2</Subscript>)<Subscript>2</Subscript> (M = Zn,Cd, Mn,Co, Ni; L = Phen, 2,2′-Bipy)

Single crystals of a mononuclear mixed-ligand complex [Mn(Phen)(i-Bu₂PS₂)₂] were grown and used for X-ray diffraction structural study of the material (diffractometer CAD-4, MoK _α -radiation, 1205 F _hkl , R = 0.0351). The crystals are monoclinic: a = 15.602(2) Å, b = 20.914(3) Å, c = 11.419(2) Å; β = 111.36(1)°, V = 3470.1(9) ų, Z = 4, ρ(calc) = 1.251 g/cm³, space group P2₁/c. Coordination polyhedron of Mn is a distorted octahedron N₂S₄. Molecular and crystal structures of mixed-ligand coordination compounds ML(i-Bu₂PS₂)₂ (M= Zn, Cd, Mn, Co, Ni; L = Phen, 2,2′-Bipy) are considered on the basis of XRD data (automated diffractometers CAD-4 and X8-APEX). The analysis of intermolecular distances in the structures of ten mixed-ligand coordination compounds revealed in nine of them the presence of short contacts made by carbon atoms of the N-heterocycles. These contacts correspond to π-π interactions of Phen or 2,2′-Bipy molecules of two neighboring complexes giving rise to dimeric molecular ensembles.     

Synthesis and structure of Cu(II) and Pd(II) coordination compounds with chiral α-thiooxime,a derivative of natural terpenoid (−)-α-pinene

The paramagnetic complex Cu(HL)Cl₂(I) (μ_eff = 1.88 μ_B) and the diamagnetic complex Pd(HL)Cl₂(II) with chiral α-thiooxime, a derivative of natural terpenoid (?)-α-pinene (HL), were synthesized. The crystal structures of these complexes were determined from single-crystal X-ray diffraction data (X8 APEX diffractometer, MoK _α radiation, 2975 F _hkl , R = 0.0258 for I and 3270 F _hkl , R = 0.0222 for II). The crystals of complex I are monoclinic, a = 9.3376(3) Å, b = 6.8619(2) Å, c = 14.6540(5) Å, β = 97.814(1)°, V = 930.22(5) ų, Z = 2, ρ_calc = 1.513 g/cm³, space group P2₁. The crystals of complex II are orthorhombic, a = 7.0084(6) Å, b = 9.2113(9) Å, c = 29.081(3) Å, V = 1877.4(3) ų, Z = 4, ρ_calc = 1.651 g/cm³, space group P2₁2₁2₁. The structures are composed of mononuclear molecules. The coordination cores MNSCl₂ (M = Cu, Pd) are tetrahedrally distorted squares. According to NMR data, complex II has a similar structure in a CDCl₃ solution. The intermolecular contacts in structure I generate supramolecular polymeric ribbons lying parallel to axis b. No short intermolecular contacts are present in complex II.     

Synthesis and structure of the mononuclear octacoordinate complex [Pb(Phen)2( iso -Bu2PS2)2] and polynuclear complex [Pb(4,4′-Bipy)( iso -Bu2PS2)2] n : Formation of ribbons and supramolecular assemblies in their crystalline structures

Heteroligand complexes [Pb(Phen)₂(iso-Bu₂PS₂)₂] (I) and [Pb(4,4′-Bipy(iso-Bu₂PS₂)₂] _n (II) were synthesized, and their crystal structures were determined. The crystals of complex I are monoclinic: a = 17.2011(9) ?, b = 14.1695(7) ?, c = 19.8727(12) ?; β = 115.644(1)°, V = 4366.5(4) ?³, Z = 4, ρ_calcd = 1.500 g/cm³, space group C2/c. The crystals of complex II are triclinic: a = 11.9283(2)?, b = 12.3814(2) ?, c = 14.0917(3) ?; α = 74.705(1)°, β = 87.240(1)°, γ = 61.448(1)°, V = 1755.86(6) ?³, Z = 2, ρ_calcd = 1.479 g/cm³, space group P . The structure of complex I consists of mononuclear molecules. The coordination polyhedron of the Pb atom is a distorted tetragonal antiprism N₄S₄ formed by the bidentate chelating ligands Phen and iso-Bu₂PS₂⁻. Continuous zigzag ribbons along the c axis are formed through contacts of the peripheral atoms of the Phen molecules of the adjacent complexes. Polynuclear complex II has a chain structure. The coordination polyhedron of the Pb atom is a distorted octahedron N₂S₄ formed by the bidentate chelating iso-Bu₂PS₂⁻ ligands and bidentate bridging 4,4′-Bipy molecules. Short intermolecular contacts between the Pb and S atoms of the adjacent chains in structure II result in the formation of supramolecular two-chain assemblies as volume columns parallel to the b axis. The environment of the Pb atoms in the assembly is formed by pentagonal bipyramids N₂S_{4 + 1}. Original Russian Text ? S.V. Larionov, R.F. Klevtsova, E.A. Sankova, L.A. Glinskaya, T.E. Kokina, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 9, pp. 1516–1524.     

Copper(II) and cobalt(II) complexes with a chiral 5-pyrazolone derivative obtained from the terpene (+)-3-carene: Synthesis and properties

The complexes [CuLCl₂] (I), [CoLCl₂] (II), and CuLBr₂ (III) (where L is the derivative of optically active 5-pyrazolone prepared from the terpene (+)-3-carene) were obtained and characterized. According to X-ray diffraction data, crystal structures I and II (orthorhombic crystal system) are built from mononuclear acentric molecules. In the resulting complexes, the Cu²⁺ or Co²⁺ ion coordinates two N atoms of the chelating bidentate ligand L and two Cl atoms, thus making a distorted tetrahedron. Intermolecular contacts and the hydrogen bonds Cl(1)…H-O(1) give rise to columns parallel to axis y. For complexes I and III, μ_eff = 1.83 and 1.81 μB, respectively; these values correspond to the electronic configuration d ⁹ . For complex II, μ_eff = 4.42 μB, which suggests the tetrahedral structure of the coordination entity CoCl₂N₂. Complexes I and III were studied by EPR spectroscopy.     

Fe(II) complex with chiral pyrazolylquinoline L and Fe(II), Co(II), and Cu(II) complexes with achiral pyrazolylquinoline L1: Synthesis and properties. The crystal structures of [ML1Cl2] (M = Fe, Co, and Cu)

The complexes FeLCl₂ (I), [FeL¹Cl₂] (II), [CoL¹Cl₂] (III), and [CuL¹Cl₂] (IV) (where L and L¹ are chiral and achiral pyrazolylquinolines, respectively) were obtained. Complexes II–IV were structurally characterized by single-crystal X-ray diffraction analysis. Crystals of complexes II and III are triclinic (space group P $ \bar 1 The complexes FeLCl₂ (I), [FeL¹Cl₂] (II), [CoL¹Cl₂] (III), and [CuL¹Cl₂] (IV) (where L and L¹ are chiral and achiral pyrazolylquinolines, respectively) were obtained. Complexes II–IV were structurally characterized by single-crystal X-ray diffraction analysis. Crystals of complexes II and III are triclinic (space group P ) and crystals of complex IV are monoclinic (space group P2₁/n). Structures II–IV are built from discrete mononuclear acentric molecules. In these complexes, the M²⁺ ion (M = Fe, Co, and Cu) coordinates two N atoms of the bidentate chelating ligand L¹ and two Cl atoms. The coordination cores MCl₂N₂ are distorted tetrahedra. For complexes I and II, μ_eff = 5.05 and 5.07 μ_B, respectively, correspond to the high-spin configuration d ⁶. For complex III, μ_eff = 4.51 μ_B (high-spin configuration d ⁷) and for complex IV, μ_eff = 1.80 μ_B (configuration d ⁹). Original Russian Text ? Z.A. Savel’eva, L.A. Glinskaya, R.F. Klevtsova, S.A. Popov, A.V. Tkachev, N.V. Semikolenova, V.A. Zakharov, S.V. Larionov, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 4, pp. 285–292.     

Influence of low temperatures on the fracture micromechanism of materials with bcc and fcc lattice structures under single loading conditions

General regularities of the influence of the local stress state of a material on the plastic zone formation at the crack tip and the fracture micromechanism of materials with bcc and fcc lattice structures under single loading (static, impact, high-speed pulsed) conditions have been established. Schemes of plastic zone formation under plane strain, plane stress, and in the transient region from plane strain to plane stress are proposed.     

Crystal structure of a new ternary molybdate Rb5CeZr(MoO4)6

A ternary salt system Rb₂MoO₄-Ce₂(MoO₄)₃-Zr(MoO₄)₂ is studied by powder XRD. Single crystals of 5:1:2 ternary rubidium-cerium-zirconium molybdate Rb₅CeZr(MoO₄)₆ are obtained by solution melt crystallization under spontaneous nucleation conditions. The crystal structure is solved by X-ray crystallography (X8 APEX automated diffractometer, MoK _?? radiation, 1274 F(hkl), R = 0.0456). The parameters of a trigonal unit cell are: a = b = 10.7248(2) ?, c = 38.796(1) ?, V = 3864.52(14) ?³, Z = 6, $R\bar 3c$ space group. The three-dimensional complex framework comprises Mo tetrahedra linked to two independent (Ce,Zr)O₆ octahedra. Two types of rubidium atoms occupy large cavities of the framework.     

CdS formation upon decomposition of Cd(n-BuOCS2)2 in EtOH and DMF and the crystal structure of Cd(Ph3P)(n-BuOCS2)2 · Ph3P

The thermal decomposition of the chelate Cd(n-BuOCS₂)₂ (I) in EtOH and DMF, either in the absence or in the presence of Ph₃P, yields finely disperse CdS particles. Mixed-ligand complex Cd(Ph₃P)(n-BuOCS₂)₂ (II) has been synthesized. Cd(Ph₃P)(n-BuOCS₂)₂ · Ph₃P (III) single crystals have been grown. By X-ray crystallography, the crystal structure of III is built of [Cd(Ph₃P)(n-BuOCS₂)₂] mononuclear complex molecules and uncoordinated Ph₃P molecules, which reside inside channels formed by complex II molecules. The coordination polyhedron around a Cd atom is a tetragonal pyramid where the base is formed by the four S atoms of the two bidentate chelating ligands n-BuOCS₂⁻ and the P atom of the Ph₃P ligand is at the axial vertex. In the structure of III, there are supramolecular assemblies of two complex II molecules.     

Synthesis and properties of the Cu(II) complexes with chiral bis{( E )-[(1 S ,4 R )-Δ7,8-1-amino-2- para -menthalidene]aminohydroxy}methane (L — a derivative of natural terpenoid ( R )-(+)-limonene). Crystal structure of the [Cu(L)(μ-Cl)CuCl3] · iso -PrOH solvate

The Cu₂LCl₄ complex (I) with chiral bis{(E)-[(1S,4R)-Δ^7,8-1-amino-2-para-menthalidene]aminohydroxy} methane (L — a derivative of natural monoterpenoid (R)-(+)-limonene) is synthesized. The crystal structure of the solvate of complex I[Cu(L)(μ-Cl)CuCl₃] · iso-PrOH (II) is determined by X-ray diffraction analysis. Structure II is based on molecules of the [Cu(L)(μ-Cl)CuCl₃] binuclear complexes in which L is the tetradentate cycleforming ligand. One Cl atom manifests the bridging function. The CuN₄ Cl coordination unit is a square pyramid, and CuCl₄ is a distorted tetrahedron. The iso-PrOH molecules are localized in cavities between the layers of structure II. The μ_eff value for complex I is 2.56 μB and indicates the absence of an appreciable interaction between the Cu²⁺ ions in the Cu(II)-Cl-Cu(II) exchange cluster. The compound CuLCl₂· H₂O (III) is synthesized. The μ_eff value for compound III is 1.6 μB. Complexes I and III are studied by EPR and IR spectroscopy. Original Russian Text ? T.E. Kokina, L.A. Glinskaya, R.F. Klevtsova, E.G. Boguslavskii, L.A. Sheludyakova, S.N. Bisyaev, A.V. Tkachev, S.V. Larionov, 2009, published in Koordinatsionnaya Khimiya, 2009, Vol. 35, No. 3, pp. 202–211.