Julia A. Rusanova

A novel fully conjugated phenanthroline-appended phthalocyanine: synthesis and characterisation

The synthetic route to a new fully conjugated phenanthroline appended phthalocyanine is described. This compound has been fully characterised by elemental analysis, UV-VIS, IR, MS and 1H NMR spectroscopy.

catena-Poly[thorium(IV)-tetrakis(μ2-3-carboxyadamantane-1-carboxylato)]: a quadruple helical strand driven by a synergy of coordination and hydrogen bonding

The title compound, [Th(C(12)H(15)O(4))(4)](n), is the first homoleptic thorium-carboxylate coordination polymer. It has a one-dimensional structure supported by the bidentate bridging coordination of the singly charged 3-carboxyadamantane-1-carboxylate (HADC(-)) anions. The metal ion is situated on a fourfold axis (site symmetry 4) and possesses a square-antiprismatic ThO(8) coordination, including four bonds to anionic carboxylate groups [Th-O = 2.359 (2) Å] and four to neutral carboxyl groups [Th-O = 2.426 (2) Å], while a strong hydrogen bond between these two kinds of O-atom donor [O...O = 2.494 (3) Å] affords planar pseudo-chelated Th{CO(2)...HO(2)C} cycles. This combination of coordination and hydrogen bonding is responsible for the generation of quadruple helical strands of HADC(-) ligands, which are wrapped around a linear chain of Th(IV) ions [Th...Th = 7.5240 (4) Å] defining the helical axis.

Unusual centrosymmetric structure of [M(18-crown-6)](+) (M = Rb, Cs and NH4) complexes stabilized in an environment of hexachloridoantimonate(V) anions.

In (1,4,7,10,13,16-hexaoxacyclooctadecane)rubidium hexachloridoantimonate(V), [Rb(C12H24O6)][SbCl6], (1), and its isomorphous caesium {(1,4,7,10,13,16-hexaoxacyclooctadecane)caesium hexachloridoantimonate(V), [Cs(C12H24O6)][SbCl6]}, (2), and ammonium {ammonium hexachloridoantimonate(V)-1,4,7,10,13,16-hexaoxacyclooctadecane (1/1), (NH4)[SbCl6]·C12H24O6}, (3), analogues, the hexachloridoantimonate(V) anions and 18-crown-6 molecules reside across -3 axes passing through the Sb atoms and the centroids of the 18-crown-6 groups, both of which coincide with centres of inversion. The Rb(+) [in (1)], Cs(+) [in (2)] and NH4(+) [in (3)] cations are situated inside the cavity of the 18-crown-6 ring; they are situated on -3 axes and are equally disordered about centres of inversion, deviating from the centroid of the 18-crown-6 molecule by 0.4808 (13), 0.9344 (7) and 0.515 (8) Å, respectively. Interaction of the ammonium cation and the 18-crown-6 group is supported by three equivalent hydrogen bonds [N...O = 2.928 (3) Å and N-H...O = 162°]. The centrosymmetric structure of [Cs(18-crown-6)](+), with the large Cs(+) cation approaching the centre of the ligand cavity, is unprecedented and accompanied by unusually short Cs-O bonds [2.939 (2) and 3.091 (2) Å]. For all three compounds, the [M(18-crown-6)](+) cations and [SbCl6](-) anions afford linear stacks along the c axis, with the cationic complexes embedded between pairs of inversion-related anions.

Crystal structure of aqua-1κO-{μ-2-[(2-hydroxy­ethyl)methylamino]ethanolato-2:1κ4O1,N,O2:O1}[μ-2,2′-(methylimino)diethanolato-1:2κ4O,N,O′:O]dithiocyanato-1κN,2κN-chromium(III)copper(II)

[Cr(μ-mdea)Cu(μ-Hmdea)(NCS)2H2O], (where mdeaH2 is N-methyldiethanolamine) is formed as a neutral heterometal CuII/CrIII complex whose molecular structure is based on a binuclear {CuCr(μ-O)2} core. In the crystal, the binuclear complexes are linked via two pairs of O—H⋯O hydrogen bonds to form inversion dimers, which are arranged in columns parallel to the a axis.

Poly[[tri-μ-aqua-do-deca-aqua-tris-(μ3-1-hy-droxy-ethyl-idene-1,1-di-phospho-nato)tricalcium(II)tripalladium(II)] penta-hydrate].

The asymmetric unit of the title compound, {[CaPd{CH3OHC(PO3)2}(H2O)5]·5/3H2O}n, consists of one half of the complex [Pd{CH3OHC(PO3)2}]2− anion (point group symmetry m..), one Ca2+ cation [site symmetry (.2.)] that is surrounded by three water molecules (one of which is on the same rotation axis) and by three disordered lattice water molecules. The anions form a trinuclear metallocycle around a crystallographic threefold rotation axis. The cations are related by a twofold rotation axis to form a [Ca2(H2O)10]2+ dimer. The slightly distorted square-planar coordination environment of the PdII atoms in the complex anions is formed by O atoms of the bidentate chelating phosphonate groups of the 1-hydroxyethylidene-1,1-diphosphonate ligands. In the crystal, cations are bound to anions through —Ca—O—P—O— bonds, as well as through O—H⋯O hydrogen bonds, resulting in a three-dimensional polymer. The structure is completed by five disordered solvent molecules localized in cavities within the 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].

Tris(2,2′-bipyridine)­copper(II) penta­cyanido­nitro­soferrate(II) methanol disolvate monohydrate

The title complex [Cu(C10H8N2)3][Fe(CN)5(NO)]·2CH3OH·H2O, consists of discrete [Cu(bpy)3]2+ cations (bpy is 2,2′-bipyridine), [Fe(CN)5NO]2− anions and solvent molecules of crystallization (two methanol molecules and one water molecules per asymmetric unit). The CuII ion adopts a distorted octahedral environment, coordinated by six N atoms from three bpy ligands. The cation charge is balanced by a nitroprusside counter-anion, which has a slightly distorted octahedral coordination geometry. In the crystal, anions and solvent molecules are involved in O—H⋯N and O—H⋯O hydrogen bonds, which form chains along [100]. The cations are located between these chains.

Bis(2,9-dimethyl-1,10-phenanthroline)copper(I) penta-cyanido-nitro-soferrate(II).

The asymmetric unit of the title complex [Cu(C14H12N2)2]2[Fe(CN)5(NO)], consists of a [Cu(dmp)2]+ cation (dmp is 2,9-dimethyl-1,10-phenanthroline) and half an [Fe(CN)5(NO)]2− anion. The anion is disordered across an inversion center with the FeII ion slightly offset (ca 0.205Å) from the inversion center in the direction of the disordered trans-coordinating CN/NO ligands. The anion has a distorted octahedral coordination geometry. The CuI ion is coordinated by two phenanthroline ligands in a distorted tetrahedral geometry. The dihedral angle between the phenanthroline ligands is 77.16 (4) Å. In the crystal, the cations are connected to the anions by weak C—H⋯N hydrogen bonds. In addition, weak π–π stacking interactions are observed, with centroid–centroid distances in the range 3.512 (3)–3.859 (3) Å.

Bis(μ-4-nitro-2-{[2-(oxidometh-yl)phen-yl]imino-meth-yl}phenolato)bis-[chlorido(dimethyl sulfoxide)-iron(III)] dimethyl sulfoxide disolvate.

In the centrosymmetric dimeric title complex, [Fe2(C14H10N2O4)2Cl2(C2H6OS)2]·2C2H6OS, two {Fe(L)Cl(DMSO)} units (L is the tridentate ligand 4-nitro-2-{[2-(oxidomethyl)phenyl]iminomethyl}phenolate; DMSO is dimethyl sulfoxide) are bridged by two O atoms, with an Fe⋯Fe separation of 3.1838 (8) Å. The coordination polyhedron of the FeIII atoms can be described as distorted octahedral, with four Fe—O, one Fe—N and one Fe—Cl coordination bonds. The L ligand is not planar, the dihedral angle between the 2-(oxidomethyl)phenyl]imino and 4-nitro-2-(iminomethyl)phenolate planes being 48.54 (9)°. The solvent DMSO molecule is disordered over two orientations with equal occupancy.

Bis[2-(hy­droxy­imino­meth­yl)phenolato]nickel(II): a second monoclinic polymorph

The title compound, [Ni(C7H6NO2)2], (I), is a second monoclinic polymorph of the compound, (II), reported by Srivastava et al. [Acta Cryst. (1967), 22, 922] and Mereiter [Private communication (2002) CCDC refcode NISALO01]. The bond lengths and angles are similar in both structures. The molecule in both structures lies on a crystallographic inversion center and both have an internal hydrogen bond. The title compound crystallizes in the space group P21/c (Z = 2), whereas compound (II) is in the space group P21/n (Z = 2) with a similar cell volume but different cell parameters. In both polymorphs, molecules are arranged in the layers but in contrast to the previously published compound (II) where the dihedral angle between the layers is 86.3°, in the title polymorph the same dihedral angle is 29.4°. The structure of (I) is stabilized by strong intramolecular O—H⋯O hydrogen bonding between the O—H group and the phenolate O atom.