Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical Investigation.

Three novel heterometallic Ni/Cd coordination compounds [Ni(en)][CdCl]∙3dmso (), [Ni(en)(dmf)][CdBr] (), and [Ni(en)][CdI](I) () have been synthesized through the self-assembly process in a one-pot reaction of cadmium oxide, nickel salt (or nickel powder), NHX (X = Cl, Br, I), and ethylenediamine in non-aqueous solvents dmso (for ) or dmf (for and ). Formation of the one- () or three-dimensional ( and ) hydrogen-bonded frameworks has been observed depending on the nature of the [CdX] counter-anion, as well as on the nature of the solvent. The electronic structures of [Ni(en)] and [Ni(en)(dmf)] cations were studied at the DFT and CASSCF levels, including the ab initio ligand field theory (AILFT) calculations.

Cation Charge as a Tool to Change Dimensionality in Organic-Inorganic Hybrids Based on Copper Thiocyanate Templated by 1,4-Diazabicyclo[2.2.2]octane.

The first three compounds based on a {copper-thiocyanate-dabco} combination, namely, (Hdabco)[Cu(NCS)] (), (Hdabco)[Cu(NCS)] (), and [Cu(Hdabco)(NCS)]∙2dmso (), where dabco = 1,4-diazabicyclo[2.2.2]octane were synthesized and characterized by single-crystal XRD, elemental analysis, Raman, and partial IR spectroscopy.

Supramolecular Diversity, Theoretical Investigation and Antibacterial Activity of Cu, Co and Cd Complexes Based on the Tridentate N,N,O-Schiff Base Ligand Formed In Situ.

The four new complexes, [Cu(HL)(L)Cl] (), [Cu(HL)(L)]∙Cl∙2HO (), [Co(L)]∙Cl () and [Cd(HL)I]∙dmso (), have been prepared by one-pot reactions of the respective chloride or iodide metal salt with a non-aqueous solution of the polydentate Schiff base, HL, resulted from in situ condensation of benzhydrazide and 2-pyridinecarboxaldehyde, while a ligand HL, in case of , has been formed due to the oxidation of 2-pyridinecarboxaldehyde under reaction conditions. The crystallographic analysis revealed that the molecular building units in - are linked together into complex structures by hydrogen bonding, resulting in 1D, 2D and 3D supramolecular architectures for , and , respectively, and the supramolecular trimer for . The electronic structures of - were investigated by the DFT theoretical calculations.

Field-induced mononuclear cobalt(II) single-molecule magnet (SMM) based on a benzothiadiazole--vanillin ligand.

A unique π-conjugated benzothiadiazole--vanillin ligand (HL), characterized by single crystal X-ray diffraction and DFT calculations, has been prepared by condensation between 4-amino-benzothiadiazole (BTD) and -vanillin. Its reaction with cobalt(II) acetate afforded the complex of formula [CoL]·CHCl (1), for which the coordination environment of the cobalt centre is a distorted octahedron and the ligand acts as a monoanionic tridentate chelate in its phenolate form. Intermolecular π-π stacking interactions between the π-conjugated BTD units provide an antiferromagnetic coupling pathway, as indicated by the analysis of the dc magnetic measurements of a crystalline sample of the complex and supported by DFT type calculations.

A bis-chelate -vanillin-2-ethano-lamine copper(II) complex bearing both imine and amine forms of the ligand.

The mol-ecular bis-chelate complex (2-{[(2-hy-droxy-ethyl-κ)amino-κ]meth-yl}-6-meth-oxy-phenolato-κ)(2-{[(2-hy-droxy-eth-yl)imino-κ]meth-yl}-6-meth-oxy-phenolato-κ)copper(II), [Cu(CHNO)(CHNO)] or [Cu(H )(H ); H = CHNO; H = CHNO, represents the first compound containing a salicyl-idene-2-ethano-lamine type ligand in both imino H (Schiff base) and amino H (reduced Schiff base) forms that has been structurally characterized on the basis of X-ray data. Two mol-ecules of the monodeprotonated ligands coordinate the Cu ion in an (, )-bidentate and an (, , )-tridentate fashion in the case of the imino and amino forms, respectively. The shape of the CuNO coordination polyhedron is a distorted square-pyramid (geometry index τ = 0.

Synthesis and crystal structure of a solvated Co complex with 2-hy-droxy-3-meth-oxy-benzaldehyde thio-semicarbazone ligands.

The title Co complex, bis-[bis-(2-hy-droxy-3-meth-oxy-benzaldehyde thio-semi-carbazonato)cobalt(III)] di-thio-nate-dimethylformamide-methanol (1/4/3), [Co(CHNOS)](SO)·4CHNO·3CHOH, with monodeprotonated 2-hy-droxy-3-meth-oxy-benzaldehyde thio-semicarbazone as ligands crystallizes in the space group . The asymmetric unit consists of two mononuclear [Co ] cations, one di-thio-nate anion (SO) as counter-anion and seven solvate mol-ecules (four di-methyl-methanamide and three methanol). Each Co ion has a moderately distorted octa-hedral SNO geometry.

Crystal structure of hexa-kis-(,-di-methyl-form-amide-κ)iron(III) μ-chlorido-bis-(tri-chlorido-cadmium).

The title compound, [Fe(CHNO)][CdCl], crystallizes in the trigonal space group and is assembled from discrete [Fe(DMF)] cations (DMF = ,-di-methyl-formamide) and [CdCl] anions. In the cation, the iron(III) atom, located on a special position of site symmetry, is coordinated by six oxygen atoms from DMF ligands with all Fe-O distances being equal [2.0072 (16) Å].

A binuclear Cu/Ca thio-cyanate complex with a Schiff base ligand derived from -vanillin and ammonia.

The new heterometallic complex, aqua-1κ-bis-(μ-2-imino-methyl-6-meth-oxy-phenolato-1κ , :2κ ,)bis-(thio-cyanato-1κ)calcium(II)copper(II), [CaCu(CHNO)(NCS)(HO)], has been synthesized using a one-pot reaction of copper powder, calcium oxide, -vanillin and ammonium thio-cyanate in methanol under ambient conditions. The Schiff base ligand (CHNO) is generated from the condensation of -vanillin and ammonia, which is released from the initial NHSCN. The title compound consists of a discrete binuclear mol-ecule with a {Cu(μ-O)Ca} core, in which the Cu⋯Ca distance is 3.

Crystal structure of imidazo[1,5-]pyridinium-based hybrid salt (CHN)[MnCl].

A new organic-inorganic hybrid salt [][MnCl] (I) where is the 2-methyl-3-(pyridin-2-yl)imidazo[1,5-]pyridinium cation, is built of discrete organic cations and tetra-chlorido-manganate(II) anions. The cation was formed in the oxidative cyclo-condensation of 2-pyridine-carbaldehyde and CHNH·HCl in methanol. The structure was refined as a two-component twin using (Spek, 2020 ▸) to de-twin the data.

Versatile coordination behaviour of the chloro-tetrazine-picolylamine ligand: mixed-valence binuclear Cu(i)/Cu(ii) complexes.

The 3-Cl-6-amino-(2'-picolyl)-1,2,4,5-tetrazine ligand HL has been synthesized and structurally characterized. Its versatile coordination behavior has been evidenced through reactions with Cu(Hfac) and Cu(triflate) precursors, which provided mixed-valence bimetallic CuCu complexes [Cu(μ-Cl)(L)] 2 and [Cu(μ-triflate)(L)] 5. Changing the Cu(ii) precursor and the solvent leads to the formation of mononuclear octahedral Cu(ii) complexes [CuCl(HL)]·2CHCN 3 and [Cu(Hfac)(HL)] 4, in which only the amino-pyridine unit is involved in the coordination of the metal center.

Co-existence of ferro- and antiferromagnetic interactions in a hexanuclear mixed-valence CoMnMn cluster sustained by a multidentate Schiff base ligand.

The successful utilization of the "direct synthesis" approach yielded the unprecedented hexanuclear complex of formula [CoMnMn(L)Cl(μ-O)(dmf)]·2dmf (1) (HL is the Schiff base derived from the condensation of salicylaldehyde and 3-aminopropane-1,2-diol). Single crystal X-ray analysis revealed that 1 crystallizes in the monoclinic system P2/c and it contains a rare mixed-valence {CoMnMn(μ-O)(μ-O)} core where all metal ions are linked through the phenolato and alkoxo groups of the L ligand. Besides the charge balance resulting from the X-ray structure, the oxidation state of the metal ions has been confirmed by XPS spectroscopy.

Details make the difference: a family of tetranuclear CuMn complexes with cube-like and double open cube-like cores.

The "direct synthesis" approach, namely one-pot reaction of metal powders and ammonium salt with a methanol solution of a polydentate Schiff base (HL) formed in situ from salicylaldehyde and ethanolamine, has been successfully used for the preparation of the new heterometallic compounds [CuMn(L)(CHOH)]I (1), [CuMn(L)(CHOH)(HO)]NCS·HO (2), [CuMn(L)(CHOH)(HO)]Br·0.45HO (3) and [CuMn(L)(HO)]BF·0.6HO (4).

Crystal structure of catena-poly[calcium-di-μ3-benzoato-κ(6) O,O':O-μ2-(dimethyl sulfoxide)-κ(2) O:O].

In the title complex, [Ca(C7H5O2)2(C2H6OS)] n , the Ca(2+) ion (site symmetry m..) is surrounded by eight O atoms, six from two bridging-chelating tridentate benzoate carboxyl groups and two from a bridging dimethyl sulfoxide mol-ecule (point group symmetry m.

Crystal structure of {2-[({2-[(2-amino-eth-yl)amino]-eth-yl}imino)-meth-yl]pheno-lato}aqua-copper(II) bromide.

In the mononuclear copper(II) title complex, [Cu(C11H16N3O)(H2O)]Br, the Cu(II) atom is coordinated by one O and three N atoms of the Schiff base ligand that forms together with one water mol-ecule a slightly distorted [CuN3O2] square-pyramidal polyhedron. The deviation of the Cu(II) atom from the mean equatorial plane is 0.182 (2) Å.

catena-Poly[[manganese(III)-bis-{μ-2-[(2-hy-droxy-eth-yl)imino-meth-yl]-6-meth-oxy-phenolato-κ(3) O (1),N:O (2);κ(3) O (2):N,O (1)}] iodide].

In the title one-dimensional coordination polymer, {[Mn(C10H12NO3)2]I} n , the potentially tetra-dentate (O,O,O,N) 2-[(2-hy-droxy-eth-yl)imino-meth-yl]-6-meth-oxy-phenol (H2 L) ligands are mono-deprotonated (as HL (-)) and coordinated by the metal ions in a tridentate chelate-bridging fashion [2.0111112]. The Mn(III) atom possesses a distorted trans-MnO4N2 octa-hedral coordination environment.

Bis(2-hy-droxy-imino-methyl-6-meth-oxy-phenolato-κ(2)N,O(1))copper(II).

In the title compound, [Cu(C(8)H(8)NO(3))(2)], the nearly planar mol-ecule (r.m.s.

Tris(2,2'-bipyridine-κN,N')cobalt(III) tris-(oxalato-κO,O)ferrate(III) mono-hydrate.

The title compound, [Co(C(10)H(8)N(2))(3)][Fe(C(2)O(4))(3)]·H(2)O, con-sists of two discrete tris-(chelate) metal ions (Co(III)N(6) and Fe(III)O(6) chromophores) and a water mol-ecule. The structure is highly symmetrical; the Co(III) and Fe(III) ions occupy positions with site symmetry 3.2.

Hexa-kis-(dimethyl-formamide-κO)manganese(II) μ-oxido-bis-[trichlorido-ferrate(III)].

The title compound, [Mn(C(3)H(7)NO)(6)][Fe(2)Cl(6)O], was obtained unintentionally as a product of an attempted synthesis of heterometallic complexes with Schiff base ligands using manganese powder and FeCl(3)·6H(2)O as starting materials. In the [Fe(2)OCl(6)](2-) anion, the O atom and the Fe atom occupy positions with site symmetry [Formula: see text] and 3, respectively, resulting in a linear Fe-O-Fe angle and a staggered conformation. The octa-hedrally surrounded cation (site symmetry [Formula: see text]) and the [Fe(2)Cl(6)O](2-) anion are alternately stacked along [001].

Structural, magnetic, high-frequency and high-field EPR investigation of double-stranded heterometallic [{Ni(en)2}2(micro-NCS)4Cd(NCS)2](n).nCH3CN polymer self-assembled from cadmium oxide, nickel thiocyanate and ethylenediamine.

A novel heterometallic 1D coordination polymer [{Ni(en)2}2(micro-NCS)4Cd(NCS)2](n) x nCH3CN (en = ethylenediamine) has been prepared using the self-assembly process in a one-pot reaction of cadmium oxide, nickel and ammonium thiocyanates with an acetonitrile solution of ethylenediamine. The complex consists of an uncommon cis-Cd(SCN)4(NCS)2(4-) fragment and a rare combination of cis-Ni(en)2(2+) and trans-Ni(en)2(2+) building blocks linked by micro(1,3)-NCS bridges into a double-stranded zigzag chain structure. Each chain is comprised of [Ni2Cd2(micro-NCS-N,S)4)] macrocycles with chair-like and rectangular-like shapes arrayed alternately.

A three-dimensional framework of bis[tris(ethylenediamine)zinc] tetraiodocadmate diiodide assisted by N-H...I hydrogen bonds.

The title salt, [Zn(C(2)N(2)H(8))(3)](2)[CdI(4)]I(2), conventionally abbreviated [Zn(en)(3)](2)[CdI(4)]I(2), where en is ethylenediamine, contains discrete [Zn(en)(3)](2+) cations and [CdI(4)](2-) anions with distorted octahedral and nearly tetrahedral geometries, respectively, as well as uncoordinated I(-) ions. The cation and the free I(-) anion lie on twofold rotation axes and the [CdI(4)](2-) anion lies on a -4 axis in the space group I-42d. The structure exhibits numerous weak inter-ionic hydrogen bonds of two types, viz.