Gervas E. Assey

Di-μ2-acetato-diacetato-bis­{μ2-3,3′,5,5′-tetra­meth­oxy-2,2-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}tricobalt(II,III) dichloro­methane disolvate

The trinuclear title compound, [Co3(CH3COO)4(C20H22N2O6)2]·2CH2Cl2, contains mixed-valence cobalt ions in the following order CoIII–CoII–CoIII where all the three cobalt ions are hexacoordinated. The central cobalt ion is situated on an inversion centre and is in an all-oxygen environment, coordinated by four phenolate O atoms and two O atoms from bridging acetate groups, while the terminal cobalt ion is hexacoordinated by two phenolate O atoms, two acetate O atoms and two imine N atoms. This complex contains a high-spin central CoII and two terminal low-spin CoIII i.e. CoIII(S = 0)–CoII(S = 3/2)-CoIII(S = 0). There are weak intermolecular C—H⋯O interactions involving the methoxy groups, as well as intermolecular C—H⋯O interactions involving the acetate anions. In addition, the dichoromethane solvate molecules are held in place by weak C—H⋯Cl interactions.

Ethyl-enediammonium tetra-kis({2,2'-[ethane-1,2-diylbis(nitrilo-methyl-idyne)]diphenolato}nickel(II)) bis-(perchlorate) dimethyl-formamide monosolvate.

The title compound, (C2H10N2)[Ni(C16H14N2O2)]4(ClO4)2·C3H7NO, crystallizes with four Ni(salen) molecules {salen is 2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolate}, one ethylenediammonium cation (actually two half-cations, each located on a center of inversion), two perchlorate anions and one dimethylformamide solvent molecule in the asymmetric unit. Each NiII cation in the Ni(salen) complex is four-coordinated by two imine N atoms and two phenolate O atoms from the tetradentate ligand. The Ni(salen) units form parallel slipped stacks with Ni⋯Ni separations of 3.4541 (4) and 3.6442 (6) Å. The crystal packing is stabilized by intermolecular hydrogen bonds between the ammonium H atoms and the perchlorate and salen O atoms, which generate a three-dimensional structure.

{3,3′,5,5′-Tetra­meth­oxy-2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}nickel(II)

The title square-planar nickel complex, [Ni(C20H22N2O6)], has Ni—N and Ni—O bond lengths of 1.8448 (14)/1.8478 (14) and 1.8536 (12)/1.8520 (12) Å. There is a slight twist in the two benzene rings at each end of the complex [dihedral angle = 11.11 (5)°]. All the atoms of the methoxy substitutents are in the plane of the ring to which they are attached except for one which deviates slightly [0.365 (3) Å]. In the crystal, weak C—H⋯O intermolecular interactions connect the molecules.

Aqua­{6,6′-dimeth­oxy-2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}methano­lmanganese(III)) perchlorate hemihydrate

The asymmetric unit of the title compound, [Mn(C18H18N2O4)(CH3OH)(H2O)]ClO4·0.5H2O, contains two complex cations and two perchlorate anions, one of which is disordered over two positions in a 0.767 (8):0.233 (8) ratio. The MnIII atoms are in distorted octahedral environments. In addition to the equatorial tetradentate salicylaldimine ligand, each Mn is axially coordinated by both a methanol and a water molecule. The complex is a dimer held together by multiple strong and weak hydrogen-bonding interactions between the coordinated water molecule on one monomer with all the phenolic and methoxy O atoms on the other monomer. In addition, the two perchlorate anions are linked by hydrogen bonds to the two methanol molecules coordinated to each Mn center. The Mn—O phenolic bond distances range from 1.868 (2) to 1.882 (2) Å while the Mn—N distances range from 1.978 (2) to 1.981 (2) Å. Mn—O distances for the axial water and methanol ligands are longer at 2.226 (2)/2.257 (2) and 2.313 (2)/2.324 (2) Å, reflecting the usual Jahn–Teller distortion as found in MnIII complexes.

catena-Poly[[[{5,5′-dimeth­oxy-2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}manganese(III)]-μ-acetato] methanol monosolvate]

The title MnIII compound, {[Mn(C18H18N2O4)(CH3COO)]·CH3OH}n, was synthesized by a reaction between manganese(II) acetate and ethylenebis(4-methoxysalicylaldimine). The structure is made up of bis(4-methoxysalicyldene)ethylenediaminatomanganese(III) units bridged by acetate groups, with Mn—N = 1.9786 (9), Mn—O = 1.8784 (10) and Mn—Oacetate = 2.056 (9) and 2.2571 (9) Å, forming a one dimensional polymer (–Mn–acetate–Mn–acetate–) along [100]. The MnIII atom is in a Jahn–Teller-distorted octahedral environment with cis angles ranging from 81.87 (4) to 96.53 (4)° and trans angles ranging from 166.11 (3) to 173.93 (3)°. The methanol solvent molecule is hydrogen bonded to the phenolate O atom. In addition to this classical hydrogen bond, there are weak C—H⋯O interactions. The structure was determined from a crystal twinned by pseudo-merohedry.

[2,2'-(2,6,9,13-Tetra-azatetra-decane-1,14-di-yl)diphenolato]iron(III) iodide.

The title FeIII complex, [Fe(C22H32N4O2)]I, contains a six-coordinate FeN4O2 cation in which the ligand is a reduced Schiff base resulting from the NaBH4 reduction of the condensation product between salicylaldehyde and 1,5,8,12-tetraazadodecane. In spite of the increased flexibility of the saturated backbone of the ligand compared to the Schiff base from which it was synthesized, the complex adopts a cis-FeN4O2 conformation for the phenolic O-atom donors, which contrasts with the trans conformation adopted by the analogous ClO4 − salt [Yisgedu et al. (2009 ▶). J. Chem. Crystallogr. 39, 315–319]. In addition to extensive N—H⋯I hydrogen bonding between the amine H atoms and the anion there is a weak C—H⋯I interaction.

Bis[μ-2-(2-pyridylmethyl­amino­meth­yl)phenolato]-κ4 N,N′,O:O;κ4 O:N,N′,O-bis­[(thio­cyanato-κN)copper(II)]

The centrosymmetric binuclear complex, [Cu2(C13H13N2O)2(NCS)2], formed via phenolate oxygen bridges, involves the CuII atoms in a distorted square-pyramidal coordination [τ = 0.197 (1)]. A Cu⋯Cu separation of 3.2281 (3) Å is observed. The in-plane Cu—Ophenolate distance [1.9342 (8) Å] is shorter than the axial distance [2.252 (8) Å]. The Cu—Namine and Cu—Npy distances are similar [2.0095 (10) and 2.0192 (10) Å, respectively]. The Cu—Nthiocyanate distance [1.9678 (11) Å] is in the range found for Cu—N distances in previously determined structures containing coordinated thiocyanate anions. There is an intermolecular hydrogen bond between the amine H atom and the S atom of a coordinated thiocyanate anion.

Di-μ-perchlorato-bis-{μ-2-[(2-pyrid-yl)methyl-amino-meth-yl]phenolato)dicopper(II) acetonitrile disolvate.

In the crystal of the dinuclear title compound, [Cu2(C13H13N2O)2(ClO4)2]·2CH3CN, the two bridging perchlorate ions chelate to the two CuII atoms in a μ-O:O′ fashion on opposite sides of the equatorial plane. The CuII ions display a distorted octahedral coordination geometry (in the usual 4 + 2 Jahn–Teller arrangement), each being coordinated by two O atoms from the two perchlorate ligands, and two N and O atoms from the reduced Schiff base ligand. The asymmetric unit contains two acetonitrile solvent molecules. In the crystal structure, in addition to N—H⋯O hydrogen bonds, there are weak C—H⋯O interactions between the perchlorate O atoms and the reduced Schiff base ligand. C—H⋯N interactions are also present.

μ-Bromido-bis{μ-2,2'-[4,7-diaza-decane-1,10-diylbis(nitrilo-methanylyl-idene)]diphenolato}tricopper(II) bromide dimethyl-formamide disolvate.

The complex molecule of the title compound, [Cu3Br(C22H28N4O2)2]Br·2C3H7NO, contains three copper atoms, two of which are five-coordinate within a square-pyramidal environment and linked by a bridging Br atom occupying the apical position in each square pyramid. The remaining Cu atom is four-coordinate but with considerable tetrahedral disortion [the dihedral angle between the two chelate planes is 69.21 (7)°]. There are two molecules of dimethylformamide (DMF) present as solvent molecules, one of which is disordered over two equivalent conformations with occupancies of 0.603 (5) and 0.397 (5). The amine H atoms are involved in both inter- and intramolecular hydrogen-bonding interactions with the Br and O atoms of the cation, as well as with the O atom of the ordered DMF molecule.

Dibromido(4,7-diazadecane-1,10-di-amine)-copper(II).

In the title compound, [CuBr2(C8H22N4)], the CuII atom is six-coordinate forming a distorted octahedral complex and is bonded to two axial bromide anions and four equatorial nitrogen donors. The equatorial Cu—N bond distances range from 2.005 (8) to 2.046 (8) Å while the axial Cu—Br distances are 2.8616 (17) and 2.9402 (17) Å, thus the six-coordinate Cu complex shows the usual Jahn–Teller distortion. All amine hydrogen atoms participate in either inter- or intramolecular hydrogen bonding to the Br anions.