Synthesis and crystal structures of nitratocobaltates Na2[Co(NO3)4], K2[Co(NO3)4], and Ag[Co(NO3)3] and potassium nitratonickelate K2[Ni(NO3)4]

The cobalt(II) and nickel(II) nitrate complexes with an island structure (Na₂[Co(NO₃)₄] (I) and K₂[Co(NO₃)₄] (II)] and a chain structure [Ag[Co(NO₃)₃] (III) and K₂[Ni(NO₃)₄] (IV)] are synthesized and investigated using X-ray diffraction. In the anionic complex [Co(NO₃)₄]^2? of the crystal structure of compound I, the Co coordination polyhedron is a twisted tetragonal prism formed by the O atoms of four asymmetric bidentate nitrate groups. In the anion [Co(NO₃)₄]^2? of the crystal structure of compound II, one of the four NO₃ groups is monodentate and the other NO₃ groups are bidentate (the coordination number of the cobalt atom is equal to seven, and the cobalt coordination polyhedron is a monocapped trigonal prism). The crystal structures of compounds III and IV contain infinite chains of the compositions [Co(NO₃)₂(NO₃)_2/2]^? and [Ni(NO₃)₃(NO₃)_2/2]^2?, respectively. In the crystal structure of compound III, seven oxygen atoms of one monodentate and three bidentate nitrate groups form a dodecahedron with an unoccupied vertex of the A type around the Co atom. In the crystal structure of compound IV, the octahedral polyhedron of the Ni atom is formed by five nitrate groups, one of which is terminal bidentate. The data on the structure of Co(II) coordination polyhedra in the known nitratocobaltates are generalized.     

Synthesis and X-ray crystallographic characterization of [Cd(NO3)2(15-Crown-5)] and [Cd(NO3)2(18-Crown-6)]

Reaction of 15-crown-5 or 18-crown-6 in 3:1 (v/v) CH₃CN:CH₃OH with Cd(NO₃)₂·4H₂O followed by slow evaporation produces [Cd(NO₃)₂(15-crown-5)] or [Cd(NO₃)₂(18-crown-6)]. Crystals of [Cd(NO₃)₂(15-crown-5)] are orthorhombic with space group Pbca and cell parameters a = 13.562(5), b = 15.941(9), and c = 15.011(7) Å at 295 K. [Cd(NO₃)₂(18-crown-6)] crystallizes in the monoclinic space group C2/c with a = 11.235(2), b = 11.196(5), c = 15.385(3) Å, and = 99.89(2)° at 295 K. The metal center in [Cd(NO₃)₂(15-crown-5)] rests atop the macrocyclic donor array with two cis-bound nitrate anions and adopts a distorted tricapped trigonal prismatic geometry. [Cd(NO₃)₂(18-crown-6)] resides on an equatorial two-fold rotation axis with Cd²⁺ coordinated in the 18-crown-6 cavity and the nitrate anions oriented in twisted trans positions.     

A Novel Structure of Bipyridine Coordinated with Copper (II): [Cu(bipy) (H2O)3] · (NO3)2

The crystal structure of the mononuclear copper (II) complex containing a 2,2′-bipyridine and three water molecules, [Cu(bipy) (H₂O)₃]. (NO₃)₂, is reported. The copper coordination polyhedron is a five-coordinated distorted pyramid.     

A Unique Example of a Co-crystal of [Co(AMTTO)2(H2O)2](NO3)2 and [Co(AMTTO)2(CH3CN)2](NO3)2 (AMTTO = 4-amino-5-methyl-1,2,4-triazol-3(2H)-thione)

A co-crystal of cobalt(II) complexes, Co(AMTTO)₂(CH₃CN)₂]²⁺(NO₃)₂. [Co(AMTTO)₂(H₂O)₂]²⁺(NO₃)₂, compound (1) was isolated from the reaction of Co(NO₃)₂?6H₂O and 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine (AMTTO) in acetonitrile as solvent. Isolated crystals were characterized by elemental analyses, IR spectroscopy as well as X-ray diffraction studies. Crystal data for 1 at 95 K revealed a monoclinic space group P2₁/n, a?=?11.7903(5), b?=?12.1279(5), c?=?14.1443(6) Å, β?=?99.244(4)°, Z?=?2, R₁?=?0.0339. Compound 1 consists of two co-crystallized Co(II) complexes [Co(AMTTO)₂(CH₃CN)₂]²⁺ and [Co(AMTTO)₂(H₂O)₂]²⁺ and four nitrate counter anions In both complexes, cobalt(II) ions are in an octahedral arrangement. Two S, N bidentate AMTTO ligands are coordinated to both Co(II) ions. The coordination sphere of Co1 is completed by two acetonitrile molecules, and these positions are occupied by water molecules for Co2.

Graphic Abstract

A co-crystal of cobalt(II) compound was isolated from the reaction of Co(NO₃)₂?6H₂O and 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine in acetonitrile as solvent.

     

Synthesis and the crystal structure of aqua-dioxo-nitrato-(2,2′,6′,2″-terpyridine)-neptunium(V) [NpO2(NO3)(terpy)(H2O)]

The crystal structure of the [NpO₂(NO₃)(Terpy)(H₂O)] complex between pentavalent neptunium and 2,2′,6′,2″-terpyridine is determined. The crystal data are as follows: a = 11.130(3) Å, b = 7.916(2) Å, c = 18.324(5) Å, β = 100.873(6)°, V = 1585.5(8) ų, Z = 4, space group is P2₁/n, R = 0.044, and wR(F ²) = 0.092. The coordination polyhedron of the Np atom is a pentagonal bipyramid whose equatorial plane includes three nitrogen atoms of the Terpy molecule and two oxygen atoms of the nitrate ion and the water molecule.     

Crystal Structure of 6,6′-dimethoxy-2,2′-diphenyl-19-crown-5 Hg(SCN)2

The crystal structure of 6,6′-dimethoxy-2,2′-diphenyl-19-crown-5 Hg(SCN)₂ has been determined from three-dimensional X-ray diffraction data. The compound crystallizes in the triclinic space group P1 (no 2) with unit cell parameters α = 9.712(6) Å, β = 11.137(7) Å, c = 14.768(12) Å, α = 86.04(5), β = 80.36(4), γ = 65.70(4), Z = 2, V= 1435(2) ų. The structure was determined by direct methods which on refinement yielded a final value of R(F) index as 0.068.     

Synthesis and Crystal Structure of a Cyano-Bridged Bimetallic Nickel(II)–Silver(I) Complex, [Ni(dmen)<Subscript>2</Subscript>{Ag(CN)<Subscript>2</Subscript>}<Subscript>2</Subscript>] · 0.5H<Subscript>2</Subscript>O

A cyano-bridged heteronuclear bimetallic complex [Ni(dmen)₂{Ag(CN)₂}₂] · 0.5H₂O (dmen = N,N′-dimethylethylenediamine) has been prepared and characterized by IR spectroscopy and X-ray Crystallography. The compound crystallizes in the monoclinic space group P2₁/c. The crystal structure of the complex consists of two independent centrosymmetric trinuclear molecules made up of a [Ni(dmen)₂] ⁺² unit linked to two [Ag(CN)₂]⁻ anions in a trans configuration. The trinuclear units are joined by hydrogen bonding to form irregular chains.     

Synthesis and crystallographic characterization of a chiral complex of (R)‐2‐(pyridin‐2‐ylmethylene)amino‐2′‐hydroxy‐1,1′‐binaphthyl(L) with hydrated nickel(II) acetate

A chiral complex of (R)‐2‐((pyridin‐2‐ylmethylene)amino)‐2′‐hydroxy‐1,1′‐binaphthyl ( L ) with hydrated nickel (II) acetate has been synthesized and spectroscopically characterized. The crystal structure of [NiL₂(CH₃OH)(CH₃COO)]CH₃COO·CH₃OH has been determined by single‐crystal X‐ray diffraction. The complex crystallizes in the orthorhombic space group P 2(1) 2(1) 2(1) with cell constants a = 15.1035 (19), b = 17.836 (2), c = 18.730 (2)Å, α = β = γ = 90.00°, Z = 4. The structure was solved by direct methods and refined to R = 0.0346 (wR₂ = 0.0863). The analytical result of the crystal structure indicates that a pair of L ligands chelate to a Ni (II) atom in an asymmetric fashion with one Ni‐N bond being longer than the other, the Ni (II) atom is further coordinated by one methanol molecule and one acetate anion to form a distorted octahedral geometry. In the crystal of the complex, the coordination cation [NiL₂(CH₃OH)(CH₃COO)]⁺, the uncoordinated methanol molecule and uncoordinated acetate anion are further assembled into one‐dimensional chain structure via intermolecular hydrogen bonds along the a‐axis. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and crystal structure of a 2D (6,3) coordination network, {[Ag(L)1.5]NO3} n [L = 1,3-bis(benzylthio)propane]

A new dithioether silver(I) complex, {[Ag(L)_1.5]NO₃} _n (1) has been prepared by the reaction of AgNO₃ with 1,3-bis(benzylthio)propane (L) in methanol/chloroform. The structure was characterized by single-crystal X-ray diffraction analysis: rhombohedral system, space group R –3c, with a =b = 15.651(7), c = 39.26(4) Å, V = 8328(1) ų, and Z = 6. The crystal structure consists of [Ag(L)_1.5]⁺ cations and NO₃ ^– anions. In 1, each silver(I) center is coordinated equivalently to three sulfur donors from three different ligands to give a trigonal-planar coordination geometry. Each L links two adjacent silver(I) centers in bis-monodentate bridging mode to form a 2D (6,3) network sheet. Furthermore, these 2D sheets are linked by the weak coordination interactions between nitrate ions and silver(I) atoms to form a 3D brick-wall framework.     

Self-assembly in transition metal complexes: structural characterization of a copper histamine nitrate [Cu(II)(him)2(NO3)2]

A new monomeric copper (II) complex with histamine (him), [Cu(II)(him)₂(No₃)₂], has been prepared by the reaction of Cu(NO₃)₂ with histaminium dichloride and its structure was determined by x-ray crystallography. The complex crystallizes in the triclinic system, space group with a = 5.7238(4), b = 8.7094(7), c = 9.2481(11) Å, = 69.693(8), = 73.242(7), = 71.050(7)°, V = 400.84(6) ų, and Z = 1. The structure consists of discrete [Cu(II)(him)₂(NO₃)₂] molecules in which the metal atom is centrosymmetrically coordinated by two histamine ligands forming an equatorial plane with Cu–N(imidazole ring) being 2.032(2) and Cu–N(NH₂ group) being 2.023(2) Å. Two O atoms from nitrate anions coordinate on the elongated axial positions with Cu–O being 2.549(2) Å. In the crystal structure, the molecules are organized by hydrogen bonds forming a two-dimensional network.     

Synthesis,crystal structure and photophysical studies on a ruthenium(II) carbonyl hydrido compound based on 2,2′‐bipyridyl‐5,5′‐dicarboxylic acid (H2bpdc)

A novel complex, namely [Ru^II(PPh₃)(CO)(H)(Hbpdc)]·2MeOH ( 1 ) (H₂bpdc = 2,2′‐bipyridyl‐5,5′‐dicarboxylic acid), has been synthesized from the reaction of H₂bpdc with [Ru^II(PPh₃)₃(CO)(H)₂] in methanol under mild condition and characterized by elemental analysis, IR spectrum, ESI mass spectrometry, and single crystal X‐ray diffraction. The structure shows that the complex crystallizes in the monoclinic space group P2₁/c with unit cell parameters a = 11.8984(13) Å, b = 16.5180(18) Å, c = 25.5322(19) Å, β = 115.302(4)°, V = 4536.6(8) ų, Z = 4. This compound features a 1‐D supramolecular chain constructed via hydrogen bonds. Its photophysical properties have been investigated in MeOH solution and in the solid state at room temperature.     

Crystal Structure of (Cr,Cu)(Sr,La)2(La,A)Cu2O8‐δ (1212‐type) and (Cr,Cu)Sr2(Y,Ce)2Cu2O10‐δ (1222‐type) Phases

Conditions of the synthesis, crystal structures, mechanical properties, electrical resistivities and magnetizations of cuprates with the general formula (Cr,Cu)(Sr,La)₂(La,A)Cu₂O_8‐δ where A=Ca or Sr of 1212‐type and (Cr,Cu)Sr₂(Y,Ce)₂Cu₂O_10‐δ of 1222‐type were investigated. The compositions of the cuprates and an amount of the impurity phases in the samples were determined. Rietveld refinement of the structure was carried out. It was found that the formal charges of Cu (FC_Cu) calculated from the electroneutrality of refined phase compositions do not achieve value optimal for the appearence of superconducting phases.     

Three‐Dimensional Structure Constructed via Hydrogen Bonds and π‐π Stacking Interaction. Crystal Structure of [Cu(AFO)2(H2O)2](ClO4)2.2(AFO).2H2O (AFO = 4,5‐Diazafluoren‐9‐one)

The structure of the title complexes [Cu(AFO)₂(H₂O)₂](ClO₄)₂.2(AFO).2H₂O (AFO = 4,5‐Diazafluoren‐9‐one)has been established by single‐crystal X‐ray diffraction. The complex crystallizes in the triclinic space group P‐1 with cell constants a = 7.659(3) Å, b = 11.066(3) Å, c = 14.203(5) Å, alpha = 75.16(3)°, β = 79.87(3)°, gamma = 85.71(3)°, Z = 1. The structure was solved by direct methods and refined to R₁ = 0.0595 (wR₂ = 0.1164). The X‐ray analysis reveals that a pair of AFO ligands chelate to a Cu(II) atom in an asymmetric fashion with one Cu‐N bond being much longer than the other, the Cu(II) atom is further coordinated by a pair of aqua ligands to form an elongated octahedral geometry. In the crystal of the complex, the mononuclear complex cations [Cu(AFO)₂(H₂O)₂]²⁺, uncoordinated AFO molecules, lattice water molecules and perchlorate anions are assembled into 3‐D structure via hydrogen bonds and π‐π stacking interaction.     

Electronic Structure of [Cu(C7H4NO3S)2(H2O)4] · 2H2O Crystal

The electronic absorption spectrum and ESR spectrum of the crystal of the title compound [Cu(C₇H₄NO₃S)₂(H₂O)₄] · 2 H₂O, are measured. The experimental results are discussed quantitatively by using the ligand field theory and the radial wave function of non-free Cu(II). The electronic structure of the compound is in agreement with its crystal structure.     

X-ray diffraction study of the heterovalent copper compound [Cu4(OH)4 Bipy 4][Cu2(B10H10)3] · 4CH3CN

X-ray diffraction studies of three samples of the [Cu₄(OH)₄ Bipy ₄][Cu₂(B₁₀H₁₀)₃]·4CH₃CN crystals reveal a small amount (4?C6%) of the second component, which is related to the main component by a mirror pseudoplane. An analysis of the geometric structure and mutual arrangement of complex cations [Cu₄(OH)₄ Bipy ₄]⁴⁺ and anions [Cu₂(B₁₀H₁₀)₃]^4? in the cell shows that replacing structural elements by their mirror equivalents results in insignificant steric conflicts. The existence of this minor crystal component can be attributed to point substitution defects or a separate twin individual.     

Crystallization of PbxSr1‐x(NO3)2 Solid Solutions from Aqueous Solutions

A series of Pb_xSr_1‐x(NO₃)₂ crystals have been grown from aqueous solutions and characterized by X‐ray powder diffraction. All diffraction data were well indexed according to the simple cubic structure. The variation of lattice constants with the concentrations of Pb²⁺ in the crystals accorded quite well to the Vegard's Law. The composition of the Sr(NO₃)₂ crystal doped with Pb²⁺ was studied by electron microprobe and it was found that Pb²⁺ was enriched in the 111 sectors. Equilibrium behavior in the Pb(NO₃)₂‐Sr(NO₃)₂‐H₂O system was analyzed by Lippmann's phase diagram and the equilibrium distribution coefficient D_Pb=133.6. This large value of D indicates that Pb²⁺ ion is preferentially distributed to the solid phase.     

Synthesis and characterization of a lead(II) complex [Pb(phen)(H<Subscript>2</Subscript>O)(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>] (phen = 1,10-phenanthroline)

The monomeric lead(II) complex, [Pb(phen)(H₂O)(NO₃)₂] was prepared by a hydrothermal reaction of Pb(NO₃)₂, nitrilotriacetic acid, NaOH, 1,10-phenanthroline, and H₂O. The structure was determined by X-ray crystallography. It crystallizes in monoclinic P2(1)/n space group with the crystal cell parameters of a = 6.3568(6), b = 20.2345(19), c = 11.2722(9) Å, β = 98.337(4)^°, V = 1434.6(2) ų, and Z = 4. The crystal X-ray analysis shows that the lead atom is six-coordinated by two N atoms of phen ligand, three oxygen atoms of nitrate anions and one water molecule. Owing to the presence of a lone pair of electrons of lead atom, a significant gap occurs in the coordination geometry around Pb ion. A 3D architecture is formed through the strong hydrogen bonding and π–π stacking interactions.     

A new organic‐inorganic molybdenum arsenate complex based on [(CuO6)(As3O3)2Mo6O18]4‐ cluster as secondary building units

A new molybdenum arsenate, [Cu(imi)₂]₂[(CuO₆)(As₃O₃)₂Mo₆O₁₈][Cu(imi)₂]₂ ( 1 ) (imi = C₃N₂H₄), has been synthesized under mild hydrothermal conditions, and characterized by elemental analysis, IR, thermogravimetric analyses, and single‐crystal X‐ray diffraction analysis. The polyanion framework derives from the Anderson structure in which the central octahedron is filled up by a copper (II), and is capped on both sides by two cyclic As₃O₆ groups. The countercations contain bisupported [Cu(imi)₂]⁺ complex cations and two free [Cu(imi)₂]⁺ complex cations. The electrochemical behavior of 1 ‐modified carbon paste electrode ( 1 ‐CPE) has been studied in detail. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and crystal structure of the [WOCl<Subscript>3</Subscript>{<Emphasis Type="Italic">Ph</Emphasis>NHC(O)CHC(O-)<Emphasis Type="Italic">Me</Emphasis>}] complex

The [WOCl₃{PhNHC(O)CHC(O⁻)Me}] complex has been synthesized, and its crystal structure has been determined. The coordination polyhedron of the tungsten atom is a distorted octahedron with a meridional arrangement of three chlorine atoms. Two oxygen atoms of the acetoacetanilide bidentate chelating ligand occupy trans positions to the O(3) oxo atom and the Cl(3) atom. The crystal structures and the IR spectra of the WOCl₃{PhNHC(O)CHC(O^t-)Me} and [MoO₂Cl₂{(o-MePh)NHC(O)CH₂C(O)Me}] complexes are compared.     

Synthesis and crystal structure of a new inorganic – organic complex: (4‐ClC7H6NH3)9[Nd(P6O18)2]·9H2O

Single crystals of (4‐ClC₇H₆NH₃)₉[Nd(P₆O₁₈)₂]·9H₂O were synthesized in aqueous solution. This compound crystallizes in a triclinic P1 unit‐cell, with a = 14.898(6), b = 18.049(7), c = 20.695(6)Å, α = 102.04(3), β = 100.49(3), γ = 98.82(3)°, V = 5245(4) ų and Z = 2. The crystal structure has been solved and refined to R = 0.043 (Rw = 0.061) for 20420 observed reflections. The atomic arrangement of the title compound can be described as infinite layers built by complex of Neodyme [Nd(P₆O₁₈)₂] and nine water molecules. The organic cations are located in the space delimited by the successive inorganic layers. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)