Valentyna V. Semenaka

Direct synthesis of an heterometallic {MnII3CrIII4} wheel by decomposition of Reineckes salt

A new heterometallic Mn/Cr molecular wheel complex has been synthesized using zerovalent manganese, Reineckes salt, ammonium thiocyanate and triethanolamine (H(3)tea) as starting materials. The compound [Mn(3)Cr(4)(NCS)(6)(Htea)(6)] (1) has been characterized in terms of its electrochemical, IR and EPR spectroscopic as well as its magnetic properties. The magnetic susceptibility and magnetization data were treated simultaneously during the optimization routine and resulted in J(Mn-Cr) = +0.43 cm(-1), J(Cr-Cr) = -4.75 cm(-1), J(Mn-Mn) = +1.78 cm(-1), g(eff) = 1.878 with the ground state S = 15/2.

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.

Diammine(2,2′-bipyridine)­bis(thio­cyan­ato­-κN)cobalt(III) diamminetetra­kis(thio­cyanato­-κN)chromate(III) aceto­nitrile disolvate

The new heterometallic title complex, [Co(NCS)2(C10H8N2)(NH3)2][Cr(NCS)4(NH3)2]·2CH3CN, has been prepared using the open-air reaction of cobalt powder, Reineckes salt and 2,2′-bipyridine (dpy) in acetonitrile. The crystal structure consists of discrete cationic [Co(NCS)2(NH3)2(dpy)]+ and anionic [Cr(NCS)4(NH3)2]− building blocks, both with 2 symmetry, and acetonitrile solvent molecules, which are linked together by N—H⋯N hydrogen bonds, forming extended supramolecular chains. Furthermore, N—H⋯S, C—H⋯S and C—H⋯N hydrogen bonds interlink neighbouring chains into a three-dimensional framework. The Co atom is in an elongated octahedral coordination environment with two N atoms from the dpy ligands and two NCS-groups in the equatorial plane and with two NH3 molecules at the axial positions. The CrIII ion is octahedraly coordinated by two NH3 molecules at the axial positions and four NCS-groups in the equatorial plane. Intensity statistics indicated non-merohedral twinning with the twin matrix [100; 00; 0]. The refined ratio of the twin components is 0.530 (1):0.470 (1).

Crystal structure of tetra­kis­[μ2-2-(di­methyl­amino)­ethano­lato-κ3N,O:O]di-μ3-hydroxido-di­thio­cyanato-κ2N-dichromium(III)dilead(II) di­thio­cyanate aceto­nitrile monosolvate

The crystal structure of the novel Pb/Cr heterometallic complex with 2-(dimethylamino)ethanol prepared by direct synthesis is reported.

trans-Chloridobis­(ethane-1,2-di­amine-κ2N,N′)(thio­cyanato-κN)cobalt(III) diammine­tetra­kis­(thio­cyanato-κN)cromate(III)

The title ionic complex [CoCl(NCS)(C2H8N2)2][Cr(NCS)4(NH3)2], which crystallizes as a non-merohedral twin, is build up of a complex cation [CoCl(NCS)(en)2]+ (en is ethane-1,2-diamine) and the Reinecke’s salt anion [Cr(NCS)4(NH3)2]− as complex counter-ion. A network of N—H⋯S and N—H⋯Cl hydrogen bonds, as well as short S⋯S contacts [3.538 (2) and 3.489 (3) Å], between the NCS groups of the complex anions link the molecules into a three-dimentional supramolecular network. Intensity statistic indicated twinning by non-merohedry with refined weighs of twin components are 0.5662:0.4338.

Hexa­kis­(dimethyl­formamide-κO)manganese(II) (dimethyl­formamide-κO)pentakis(­thio­cyanato­-κN)chromate(III)

The title compound, [Mn(C3H7NO)6][Cr(NCS)5(C3H7NO)], was obtained unintentionally as a product of an attempted synthesis of heterometallic complexes based on Reineckes anion using manganese powder, Reineckes salt and 1-(2-hydroxyethyl)tetrazole as starting materials. The crystal structure of the complex consists of an [Mn(dmf)6]2+ cation and a [Cr(NCS)5(dmf)]2− anion (dmf = dimethylformamide). The MnII and CrIII atoms show a slightly distorted octahedral MnO6 and CrN5O coordination geometries with adjacent angles in the range 85.29 (13)–95.96 (14)°.

Tris(1,10-phenanthroline-κ2N,N′)iron(II) bis­[(1,10-phenanthroline-κ2N,N′)tetra­kis­(thio­cyanato-κN)chromate(III)] acetonitrile tris­olvate monohydrate

Single crystals of the title heterometallic compound, [Fe(C12H8N2)3][Cr(NCS)4(C12H8N2)]2·3CH3CN·H2O or [Fe(Cphen)3][Cr(NCS)4(phen)]2·3CH3CN·H2O, were prepared using the one-pot open-air reaction of iron powder, Reineckes salt and 1,10-phenanthroline (phen) in acetonitrile. The asymetric unit consists of an [Fe(phen)3]2+ cation, two [Cr(phen)(NCS)4]− anions, three acetonitrile solvent molecules and a water molecule. The Fe and Cr atoms both show a slightly distorted octahedral FeN6 and CrN6 coordination geometry with adjacent angles in the range 79.67 (12)–95.21 (12)°. No classical hydrogen bonding involving the water molecule is observed.

Bis{μ2-2-[(2-hy­droxy­eth­yl)(meth­yl)amino]­ethano­lato}bis­(μ3-N-methyl-2,2′-aza­nediyldiethano­lato)tetra­kis­(thio­cyan­atato-κN)dichromium(III)dimanganese(II) dimethyl­formamide tetra­solvate

The heterometallic title complex, [Cr2Mn2(C5H11NO2)2(C5H12NO2)2(NCS)4]·4C3H7NO, was prepared using manganese powder, Reineckes salt, ammonium thiocyanate and a non-aqueous solution of N-methyldiethanolamine in air. The centrosymmetric molecular structure of the complex is based on a tetranuclear {Mn2Cr2(μ-O)6} core. The tetranuclear complex molecule and the two uncoordinated dimethylformamide molecules are linked by O—H⋯O hydrogen bonds, while the two other molecules of dimethylformamide do not participate in hydrogen bonding.