A new co-crystal dinuclear/trinuclear ZnII-ZnII/ZnII-SmIII-ZnII complex with a salen-type Schiff base ligand.

In the penta-nuclear title complex, [SmZn2(C22H18N2O4)2(NCS)2(C3H7NO)2][Zn2(C22H18N2O4)(NCS)3]·C3H7NO·0.32H2O, namely bis-{µ2-6,6'-dimeth-oxy-2,2'-[phenyl-ene-1,2-diylbis(nitrilo-methanylyl-idene)]diphenolato}-1κ4 O,N,N',O':2κ3 O,O',O 6;2κ3 O,O',O 6:3κ4 O,N,N',O'-bis-(di-methyl-formamide-2κO)di-thiocyanato-1κN,3κN-2-samarium(III)-1,3-dizinc(II) {µ2-6,6'-dimeth-oxy-2,2'-[phenyl-ene-1,2-diylbis(nitrilo-methanylyl-idene)]diphenolato-1κ4 O,N,N',O':2κ2 O,O'}trithio-cyan-ato-1κN;2κ2 N,N-dizinc(II) di-methyl-formamide monosolvate 1.32-hydrate, a dinuclear unit and a trinuclear unit co-exist. One of the ZnII centers in the dinuclear unit as well as the two ZnII centers in the trinuclear unit are located in the inner N2O2 cavity of the ligand and are coordinated to the nitro-gen atom of one thio-cyanate moiety, giving rise to a square-pyramidal geometry. The second ZnII center in the dinuclear unit is coordinated to the two phenolate oxygen atoms of the ligand and to two thio-cyanate groups via the nitro-gen atom in a tetra-hedral geometry. The SmIII ion is eight-coordinated by four phenolate O atoms from the two ligand mol-ecules, two meth-oxy O atoms from the two ligand mol-ecules and two O atoms from the DFM solvent mol-ecule. In the dinuclear unit, the two meth-oxy oxygen atoms remain uncoordinated while in the trinuclear unit, for each ligand one meth-oxy oxygen is coordinated and the other one remains uncoordinated. In the crystal, the trinuclear cationic units and dinuclear anionic units are assembled into infinite layers. These layers are held together via electrostatic inter-actions, forming a three-dimensional structure. In the dinuclear unit, the C and S atoms of one of the thio-cyanate groups are disordered over two sets of sites in a 0.680 (4)(4):0.320 (4) ratio.

Crystal structure of aqua-chlorido-(nitrato-κ2O,O')[1-(pyridin-2-yl-κN)-2-(pyridin-2-yl-methyl-idene-κN)hydrazine-κN2]manganase(II).

The search for novel manganese(II) compounds having inter-esting magnetic properties, using 1-(pyridin-2-yl)-2-(pyridin-2-yl-methyl-idene)hydrazine (HL) as a tridendate ligand, led to the preparation of the title mononuclear material, [MnCl(NO3)(C11H10N4)(H2O)], and the determination of its structure by XRD. The asymmetric unit comprises a discrete mol-ecule in which the cation MnII is hepta-coordinated. The environment around the cation is an almost perfect penta-gonal bipyramid. The base is defined by the two N atoms of the pyridine rings, the N atom of the imino function of the ligand and the two O atoms of the chelating bidentate nitrate ligand. The apical positions are occupied by a Cl atom and a water mol-ecule. In the crystal, there are numerous hydrogen bonds of the types Ow-H⋯ONO2 and C-H⋯ONO2, which generate layers parallel to the bc plane in which the ligands in the axial positions point into the inter-layer space. These axial ligands give rise to hydrogen bonds of the types Ow-H⋯ONO2, Ow-H⋯Cl, N-H⋯Cl and C-H⋯Cl, leading to a three-dimensional framework. The chain bridging the two pyridine rings is disordered over two sets of sites in a 0.53 (2):0.47 (2) ratio.