Svitlana R. Petrusenko

Direct synthesis and crystal structure of zinc thiocyanate complexes with 1,4diazabicyclo(2,2,2)octane

Abstract A direct method of synthesis of zinc thiocyanate complexes with 1,4-diazabicyclo(2,2,2) octane (or triethylenediamine, Ten) is reported. The main peculiarities of interaction of zinc oxide with non-aqueous (methanol, acetonitrile, N,N-dimethylformamide = DMF, dimethylsulfoxide = DMSO) solutions of ammonium thiocyanate in the presence of Ten were investigated. The crystal structures of the compounds [Zn2(NCS)4(NH3)2Ten] (I), (HTen)2[Zn(NCS)4] (II) and [Zn(NCS)2(Ten)DMSO] (III) were determined by X-ray diffraction. The complexes contain four (I) and five (III) coordinate zinc atoms linked by μ2-bridging nitrogen atoms of Ten forming the dimeric and polymeric molecules respectively; the complex (II) has an ionic-type crystal lattice with (HTen)+ cations and [Zn(NCS)4]2− anions.

Novel heterometallic Cu/Cd complex containing a unique polymeric ladder-like anion [Cd 2 (O 2 CMe) 6 ] 2¿ n derived from elemental copper and cadmium oxide

Abstract Copper powder reacts with cadmium oxide and ammonia acetate in methanol solution of ethylenediamine affording {[Cu(en)2][Cd2(O2CMe)6]}n in which seven-coordinated cadmium atoms are ligated by three bonding modes of acetate groups forming ladder-like anions [Cd2(O2CMe)6]2−n. The cations [Cu(en)2]2+ are located in the lattice and serve as bridges to connect separate anionic polymer chains into a two- dimensional network via hydrogen bonds.

First heterobimetallic MnII/MII(M = Cu, Ni) complexes with open-chain aliphatic schiff-base ligands obtained by direct template synthesis

Four new heterobimetallic complexes [CuL1][MnCl4] (1), [CuL2][MnCl4] (2), [NiL1][MnCl4] (3), [NiL2][MnCl4] (4) (L1 = 4,6,6-trimethyl-1,9-diamino-3,7-di-aza-nona-3-ene; L2 = 1,15-dihydroxy-7,9,9-trimethyl-3,6,10,13-tetra-aza-pentadeca-6-ene) have been prepared from elemental metals, ethylenediamine dihydrochloride or its N-(2-hydroxyethyl) derivative and acetone by the template condensation reaction. All complexes have been characterized by elemental analysis, IR and UV-Visible spectroscopy. The structures of 2 and 3 have been determined by X-ray crystallography (2: Orthorhombic, Pna2 1, a = 20.136(4), b = 11.185(2), c = 10.251(2)Å, Z = 4; 3: Orthorhombic, Pca2 1, a = 14.335(2), b = 11.405(2), c = 11.154(2)Å, Z = 4 ). Both crystals consist of alternating complex cations [ML]2+ and anions [MnCl4]2− linked together by N–H···Cl–Mn and O–H···Cl–Mn hydrogen bonds forming 2D corrugated sheets in (2) and 1D helical chains in (3). Complex 2 represents the first single crystal structure elucidation of the complex containing L2.

Tris(2,2′-bipyridine-κ2N,N′)cobalt(III) tris­(oxalato-κ2O1,O2)ferrate(III) mono­hydrate

The title compound, [Co(C10H8N2)3][Fe(C2O4)3]·H2O, consists of two discrete tris(chelate) metal ions (CoIIIN6 and FeIIIO6 chromophores) and a water molecule. The structure is highly symmetrical; the CoIII and FeIII ions occupy positions with site symmetry 3.2. The coordination polyhedra of the metal atoms have a nearly octahedral geometry with noticeable trigonal distortions. The Co—N and Fe—O bond lengths are equal by symmetry, viz. 1.981 (2) and 1.998 (4) Å, respectively. The cations and anions are arranged alternately along their threefold rotation axes parallel to [001], forming chains that are packed in a hexagonal manner. The water molecules occupy voids between the chains. The crystal under investigation was an inversion twin.

Direct Synthesis of Zinc and Nickel(II) Complexes with 1,4-Diazabicyclo[2.2.2]octane

Abstract The peculiarities of the formation of zinc and nickel(II) complexes by interaction of metal powder or metal oxide with ammonium salts (halides, nitrate, thiocyanate) were investigated in non-aqueous solutions (methanol, acetonitrile, N,N-dimethylformamide=DMF, dimethylsulfoxide=DMSO) in presence of 1,4-diazabicyclo[2.2.2]octane. The stoichiometry of the com plexes was found to depend on the initial reagent ratio Ni/ZnO:NH4X and Ni/ZnO:Ten. The compounds of compositions Zn(HTen)(H2O)(NO3)3 and Ni(HTen)(Ten)Cl3 were characterized by X-ray crystallography. Both complexes contain five-coordinate metal atoms. The zinc compound possesses monomeric molecular structure whilst the nickel complex is polymeric.

catena-Poly[[manganese(III)-bis­{μ-2-[(2-hy­droxy­eth­yl)imino­meth­yl]-6-meth­oxy­phenolato-κ3O1,N:O2;κ3O2:N,O1}] iodide]

In the title one-dimensional coordination polymer, {[Mn(C10H12NO3)2]I}n, the potentially tetradentate (O,O,O,N) 2-[(2-hydroxyethyl)iminomethyl]-6-methoxyphenol (H2 L) ligands are mono-deprotonated (as HL −) and coordinated by the metal ions in a tridentate chelate-bridging fashion [2.0111112]. The MnIII atom possesses a distorted trans-MnO4N2 octahedral coordination environment. The bridging ligands lead to [010]-chain polymeric cations {[Mn(HL)2]+}n in the crystal. The charge-balancing iodide ions are disordered over two sites in a 0.690 (2):0.310 (2) ratio and a weak O—H⋯I hydrogen bond occurs. The crystal studied was found to be a racemic twin.

Bis(2-hy­droxy­imino­methyl-6-meth­oxy­phenolato-κ2N,O1)copper(II)

In the title compound, [Cu(C8H8NO3)2], the nearly planar molecule (r.m.s. deviation = 0.037 Å) is centrosymmetric with the CuII atom lying on an inversion center. The CuII atom is tetracoordinated, displaying a slightly distorted square-planar geometry. The main deviation from the ideal geometry is seen in the differences in the Cu—O [1.8833 (10) Å] and Cu—N [1.9405 (13) Å] bond lengths, while angular deviations are less than 3°. Intramolecular O—H⋯O and intermolecular Csp2—H⋯O hydrogen bonds form S(5) and R 2 2(8) ring motifs, respectively. The latter interaction results in chains of molecules along [100].

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. N-H...I(-)(free ion) and N-H...I([CdI(4)](2-)), which support the resulting three-dimensional framework.

Crystal structure of {2-[({2-[(2-amino­eth­yl)amino]­eth­yl}imino)­meth­yl]pheno­lato}aqua­copper(II) bromide

In the mononuclear copper(II) title complex, [Cu(C11H16N3O)(H2O)]Br, the CuII atom is coordinated by one O and three N atoms of the Schiff base ligand that forms together with one water molecule a slightly distorted [CuN3O2] square-pyramidal polyhedron. The deviation of the CuII atom from the mean equatorial plane is 0.182 (2) Å. The equatorial plane is nearly coplanar to the aromatic ring of the ligand [angle between planes = 10.4 (1)°], and the water molecule is situated in the apical site. All coordinating atoms (except the imine nitrogen) and the bromide ion contribute to the formation of the N—H⋯Br, O—H⋯Br and O—H⋯O hydrogen bonds, which link molecules into chains along [01-1].

Hexa­kis­(dimethyl­formamide-κO)manganese(II) μ-oxido-bis­[trichlorido­ferrate(III)]

The title compound, [Mn(C3H7NO)6][Fe2Cl6O], was obtained unintentionally as a product of an attempted synthesis of heterometallic complexes with Schiff base ligands using manganese powder and FeCl3·6H2O as starting materials. In the [Fe2OCl6]2− anion, the O atom and the Fe atom occupy positions with site symmetry and 3, respectively, resulting in a linear Fe—O—Fe angle and a staggered conformation. The octahedrally surrounded cation (site symmetry ) and the [Fe2Cl6O]2− anion are alternately stacked along [001].