Crystal structures and magnetic properties of two isomorphic nickel(II) and cobalt(II) coordination polymers-based nitrogen-heterocyclic tricarbolylate ligands

5-(3,4-Dicarboxylphenyl) picolinic acid (H₃dppa) was applied as a new building block for the synthesis of two isomorphic coordination polymers, namely [Ni_1.5dppa(H₂O)₃]_n·nH₂O (1), [Co_1.5dppa(H₂O)₃]_n·nH₂O (2). Two compounds were generated by a hydrothermal self-assembly method using the corresponding metal(II) acetates and H₃cppa ligand. Structure analysis reveals that compounds 1 and 2 are isomorphic both featuring a two-dimensional wave structure and are finally extended into the three-dimensional supramolecular architecture though hydrogen bonding interactions. Magnetic susceptibility measurements indicate that domain a weak ferromagnetic exchange coupling between the adjacent Ni(II) centers in 1, and a weak antiferromagnetic coupling between Co(II) ions in for 2.

     

Three-dimensional nickel(II) and cobalt(II) coordination polymers constructed from 2,5-dichloroterephthalic acid and bis(imidazole) ligands

Two ternary mixed-ligand coordination polymers (CPs), namely [Ni(L)₂(DCTP)] _n (1) and [Co(L)(DCTP)] _n (2), have been hydrothermally synthesized by reacting different transition metal salts with 2,5-dichloroterephthalic acid (H₂DCTP) and 4,4′-[bis(imidazol-1-ylmethylene)]biphenyl (L) as ligands. Both CPs 1 and 2 were characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction; CP 1 exhibits a non-interpenetrated six-connected α-Po (or pcu net) framework structure, with the point symbol {4¹²·6³}. CP 2 shows a fivefold-interpenetrating four-connected sqc6 topology with the point symbol {6⁶}. The thermal stabilities, luminescence and catalytic properties of both CPs for the degradation of methyl orange in a Fenton-like process have been investigated.     

DSC determination of the sublimation enthalpy of tris(2,4-pentanedionato)cobalt(III) and bis(2,4-pentanedionato) nickel(II) and -copper(II)

The sublimation enthalpies of tris(2,4-pentanedionato)cobalt(III) and bis(2,4-pentahedionato)nickel(II) and -copper(II) have been determined by differential scanning calorimetry as 142.6 ± 6.9, 108.2 ± 4.9 and 107.1 ± 5.7 kJ mol⁻¹, respectively. An assessment of the sublimation characteristics of tris(2,4-pentanedionato)manganese(III) is also reported.     

Synthesis,characterization, and crystal structures of 2D cobalt(II) and nickel(II) coordination polymers containing flexible bis(benzimidazole) ligands

Three coordination polymers, namely {[Ni(L1)(nip)(H₂O)]·2H₂O} _n (1), [Co(L2)(tbip)] _n (2), and {[Co₂(L3)₂(bptc)]·3H₂O} _n (3) (L1 = 1,4-bis(5,6-dimethylbenzimidazole)butane, L2 = 1,4-bis(5,6-dimethylbenzimidazole)-2-butylene, L3 = 1,3-bis(5,6-dimethylbenzimidazole)propane, H₂nip = 5-nitro-isophthalic acid, H₂tbip = 5-tert-butyl-isophthalic acid, H₄bptc = biphenyl-3,3′,4,4′-tetracarboxylic acid), have been synthesized under hydrothermal conditions and characterized by physicochemical and spectroscopic methods as well as by single-crystal X-ray diffraction analysis. Complexes 1 and 2 both feature a two-dimensional (4,4) layer with (4⁴ × 6²) topology. Complex 3 possesses a uninodal 4-connected 2D htb network. The fluorescence spectra and catalytic properties of the complexes for the degradation of methyl orange by sodium persulfate in a Fenton-like process are reported.     

Synthesis and crystal structure of tris(ethylenediamine)cobalt(III) bis(tetrachloroaurate(III)) chloride

The binary complex salt [Co(N₂C₂H₈)₃][AuCl₄]₂Cl has been synthesized. Its crystal structure has been determined. Crystal data for C₆H₂₄N₆Cl₉AuCo: a = 20.8976(14) Å, b = 14.4773(9) Å, c = 7.9944(5) Å; β = 110.809(2)°; V = 2260.9(3) ų, space group C2/c, Z = 4, d _calc = 2.798 g/cm³. The plane square environment of the gold atom of the complex anion is completed to a tetragonal pyramid by the chlorine atom of the neighboring complex anion (Au…Cl 3.538 Å). The structure is layered. Layers of complex cations and complex anions alternate along the X axis.     

Synthesis,structures and characterization of two cobalt(II) coordination polymers with 2,5-dichloroterephthalic acid and flexible bis(benzimidazole) ligands

Two Co(II) coordination polymers (CPs), namely [Co(L1)(DCTP)]_n (1) and [Co(L2)(DCTP)]_n (2) [L1?=?1,4-bis(5,6-dimethylbenzimidazol-1-yl)butane, L2?=?1,5-bis(5,6-dimethylbenzimidazol-1-yl)pentane, H₂DCTP?=?2,5-dichloroterephthalic acid] were synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis, powder X-ray diffraction (PXRD) and infrared spectroscopy. CP 1 has a 2D (4,4) corrugated sheet structure, which is further extended into a 2D double layer by C–H···O weak hydrogen bonding interactions, while CP 2 displays a 2D layer with hcb network, which is assembled into a 3D supramolecular framework through C–H···O hydrogen bonding. Both CPs exhibited promising photocatalytic activities for the degradation of methylene blue under UV irradiation. In addition, the thermal stabilities and the luminescence properties of both CPs have been investigated.     

Extraction of cobalt (II) and nickel (II) by a solvent impregnated resin containing bis(2,4,4-trimethylpentyl)monothiophosphinic acid

In the present work, studies have been conducted on the equilibrium distribution of cobalt (II) and nickel (II) between aqueous hydrochloric solution and macromolecular resin impregnated with bis(2,4,4-trimethylpentyl)monothiophosphinic acid (Cyanex302, HL). Effects of extraction time, pH values, metal ion concentration, and temperature were investigated. Analysis of the results shows that the extraction of the two metal ions can be explained assuming the formation of metal complexes in the resin phase with a general composition ML ₂. An extraction reaction is proposed and the equilibrium constants of the complexes were determined. The Freundlich isotherm and thermodynamic quantities, i.e., ΔG, ΔH and ΔS were also obtained. Both of the extraction reactions of cobalt (II) and nickel (II) are endothermic ones. The efficiency of the resin in the separation of cobalt (II) and nickel (II) is provided according to the separation factors. Under the experimental conditions employed, pH₅₀ values for cobalt (II) and nickel (II) are 3.76, 5.01, respectively. The logarithmic value of separation factor was calculated as 2.50.     

Crystal structure of bis(iso-maleonitril-edithiolate)nickel(II) benzylpiperidinium

Bis(iso-maleonitriledithiolate)nickel(II) benzylpiperidinium, [BzPid]₂[Ni(i-mnt)₂] (1) is prepared and characterized by elemental analyses, UV, IR, molar conductivity, and single crystal X-ray diffraction. It is found that 1 crystallizes in the monoclinic space group P2₁/n with a = 9.551(1) Å, b = 16.520(2) Å, c = 11.004(1) Å, β = 96.60(1)°, V = 1724.6(3) ų, Z = 2. Consolidate the stacking of the molecules The electrostatic interaction between [Ni(i-mnt)₂]^2? anions and [BzPid]⁺ cations consolidates the stacking of the molecules.     

Ni(II) N4-macrocycle grafted crown ether: caesium cobalt(III) bis(dicarbollide) coordination polymer

A mixture of a Ni(TMTAA) grafted crown ether and Cs[Co(C2B9H11)2] in toluene-CH2Cl2 affords a 1:1 complex, comprised of layers of infinite two-dimensional polymeric arrays separated by layers of the cobalticarborane anion which themselves form two B-H...Cs+ hydrogen interactions.     

Crystal and molecular structures of bis(2,2,6,6-tetramethyl-3-methylaminoheptan-5-onate) copper(II) and nickel(II)

Two bis-chelates M(tmih)₂ (M = Cu(II), Ni(II), tmih = (CH₃)₃C(NCH₃)CHCOC(CH₃)₃)^? are synthesized and their crystal structures are determined using XRD (Bruker APEX-II diffractometer with a CCD detector, λMoK _α, λCuK _α, graphite monochromator, T = 240(2) K and 296(2) K): Cu(tmih)₂ (I) (space group P2₁/c, a = 12.9670(8) Å, b = 18.4921(9) Å, c = 11.0422(6) Å, β = 93.408(4)°, V = 2643.1(3) ų, Z = 4) and Ni(tmih)₂ (II) (space group P2₁/c, a = 12.810(2) Å, b = 18.529(2) Å, c = 11.243(2) Å, β = 91.959(7)°, V = 2667.1(6) ų, Z = 4). The complexes are isostructural; the coordination polyhedron of metal atoms is a flattened tetrahedron formed from two O atoms (Cu-O of 1.901(2) Å, 1.892(2) Å, Ni-O of 1.845(2) Å, 1.833(2) Å) and two N atoms (Cu-N of 1.976(3) Å, 1.972(3) Å, Ni-N of 1.911(2) Å, 1.920(2) Å) of the ligand; the chelate OMN angles (M = Cu(II), Ni(II)) are in the 87.4–93.1° range; the OMO and NMN angles are 162.2° and 167.2° in I, 171.1° and 173.2° in II. The complexes have the molecular structures formed from isolated molecules bonded by van der Waals interactions. Using a quantum chemical hybrid M06 method, the structures of copper(II) chelates with the H, CH₃, CH₂CH₃, CH(CH₃)₂, and C(CH₃)₃ substituents at the nitrogen atom are calculated. Found that with a bulky substituent at the nitrogen atom, the formation of chelates is hindered due to the intraligand repulsion between the atoms of this substituent and the tert-butyl group.     

Redox-active nickel and cobalt tris(pyrazolyl)borate dithiocarbamate complexes: air-stable Co(II) dithiocarbamates

A series of new cobalt(II) and nickel(II) tris(3,5-diphenylpyrazolyl)borate (Tp(Ph2)) dithiocarbamate complexes [Tp(Ph2)M(dtc)] (M = Co, dtc = S?CNEt? 1, S?CNBz? 2 and S?CN(CH?)? 3; M = Ni, dtc = S?CNEt? 4, S?CNBz? 5 and S?CN(CH?)? 6) have been prepared by the reaction of [Tp(Ph2)MBr] with Nadtc in CH?Cl?. IR spectroscopy indicates that the Tp(Ph2) ligand is κ3 coordinated while the dithiocarbamate ligand is κ2 coordinated. 1H NMR and UV-Vis spectroscopy are consistent with high spin, five-coordinate metal centres. X-ray crystallographic studies of 1, 3 and 6 confirm the κ3 coordination of the Tp(Ph2) ligand and reveal an intermediate five-coordinate geometry with an asymmetrically coordinated dithiocarbamate ligand. Electrochemical studies of 1-6 reveal a metal centred reversible one-electron oxidation to M(III). Attempted oxidation of [Tp(Ph2)Co(dtc)] with [FeCpCp(COMe)]BF? yields [Co(dtc)?], Hpz(Ph2) and a further product which may be [Tp(Ph2)CoBp(Ph2)]. DFT calculations indicate that the low redox potentials in these complexes result from a strongly antibonding M-S σ* HOMO.     

Synthesis and structure of dimeric bis(isothiocyanato)tris (4-methylpyridine)nickel (II)

Summary The Ni₂(NCS)₄(4-Methylpyridine)6 complex has been prepared crystalline from methanolic solutions of Ni(NCS)2(4-Methylpyridine)4. Three dimensional x-ray diffraction data were collected by means of an automated single crystal diffractometer. The structure was solved by Patterson methods and refined to a final R value of 0.075, based on 2422 observed_ reflections. The compound crystallizes in space group P1 with one dimeric molecule in a unit cell of dimensions a = 10.57(1), 6 = 14.06(1), c = 8.66(1) Å, = 105.2(1), = 114.8(1), y = 95.6(1)°. The Ni atoms have distorted octahedral coordination with one sulfur and five nitrogen atoms - two of the four thiocyanate groups form a double bridge between the neighbouring Ni atoms.4-MePy = 4-Methylpyridine     

Effect of organic bicarboxylates on the structures of cobalt(II) coordination polymers derived from a semi-rigid bis(benzimidazole) derivative

Two new Co(II) coordination polymers, [Co(L)(glu)] (1) and [Co(L)(npht)]·H₂O (2) (H₂glu = glutaric acid, H₂npht = 3-nitrophthalic acid, L = 1,4-bis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene), have been hydrothermally synthesized by self-assembly of cobalt chloride with a semi-rigid bis(benzimidazole) derivative and different organic bicarboxylic acids. Single crystal X-ray diffraction analysis reveals that complex 1 is a one-dimensional tube-like coordination polymer containing one helical [Co-L] and two linear [Co-glu] chains. In complex 2, two npht ligands connect two Co(II) atoms to form a binuclear [Co(npht)]₂ subunit, which is further linked by L ligands with two kinds of conformations to form a 3-D CdSO₄-like framework. In addition, the electrochemical behaviors of the title complexes in bulk-modified carbon paste electrodes, and their thermal stabilities and fluorescent properties were investigated in this paper.     

Interwoven 2-D coordination network prepared from the molecular host tris(isonicotinoyl)cyclotriguaiacylene and silver(I) cobalt(III) bis(dicarbollide)

A new 3-fold symmetric molecular host, tris(isonicotinoyl)cyclotriguaiacylene, has been synthesized from cyclotriguaiacylene and isonicotinoyl chloride hydrochloride in 70% yield. Its crystal structure shows dimerization of the host molecules into a capsule-like arrangement. When reacted with Ag[Co(C(2)B(9)H(11))(2)], the host forms a 1-D [ML(2)](n) coordination polymer, which assembles into a 2-D interwoven network through a similar dimerization of the host moieties around acetonitrile guests. Thus, the network structure represents an elegant example whereby the solid state structure of the building blocks is echoed in the resulting supramolecular assembly. The 2-D sheets are further stabilized by pi...pi stacking interactions between pyridyl donors of alternate 1-D coordination polymers.     

Syntheses of tris(t-butylisocyanide)bis(tri-p-dimethyl- aminophenylphosphine)cobalt(I) and cobalt(II) perchlorates: a reversal of the usual stabilities of cobalt oxidation states

The complexes [Co(CNCMe₃)₃{P(C₆H₄NMe₂-p)₃}₂](ClO₄)₂ and [Co(CNCMe₃)₃{P(C₆H₄NMe₂ -p)₃}₂]ClO₄ are reported. The Co(II) complex, formed by reaction of excess triarylphos-phine with the alkylisocyanide Co(II) complex, is stable and the favoured product. The Co(I) complex, formed by hydrazine reduction of the Co(II) complex, has limited stability in solution, readily oxidizing to the Co(II) species. Upon prolonged irradiation of the Co(II) complex in acetone, [Co{OP(C₆H₄NMe₂-p)₃}₄](ClO₄)₂ is produced.     

Novel adducts of ethanedialdioxime with halides of nickel(II) and cobalt(II)

Summary Ethanedialdioxime (glyoxime, gH₂) readily combines with dry CoCl₂, NiCl₂, and NiBr₂ in non-aqueous medium to yield the novel adducts CoCl₂(gH₂), NiCl₂(gH₂), and NiBr₂(gH₂). Synthesis, conventional characterization and magnetic moment data collected in the temperature range 95–293 K are reported for these diamagnetic adducts.