Crystal structure of tetra-kis-[µ2-2-(di-methyl-amino)-ethano-lato-κ(3) N,O:O]di-µ3-hydroxido-di-thio-cyanato-κ(2) N-dichromium(III)dilead(II) di-thio-cyanate aceto-nitrile monosolvate.

The tetra-nuclear complex cation of the title compound, [Cr2Pb2(NCS)2(OH)2(C4H10NO)4](SCN)2·CH3CN, lies on an inversion centre. The main structural feature of the cation is a distorted seco-norcubane Pb2Cr2O6 cage with a central four-membered Cr2O2 ring. The Cr(III) ion is coordinated in a distorted octa-hedron, which involves two N atoms of one bidentate ligand and one thio-cyanate anion, two µ2-O atoms of 2-(di-methyl-amino)-ethano-late ligands and two µ3-O atoms of hydroxide ions. The coordination geometry of the Pb(II) ion is a distorted disphenoid, which involves one N atom, two µ2-O atoms and one µ3-O atom. In addition, weak Pb⋯S inter-actions involving the coordinating and non-coordinating thio-cyanate anions are observed. In the crystal, the complex cations are linked through the thio-cyanate anions via the Pb⋯S inter-actions and O-H⋯N hydrogen bonds into chains along the c axis. The chains are further linked together via S⋯S contacts. The contribution of the disordered solvent aceto-nitrile mol-ecule was removed with the SQUEEZE [Spek (2015 ▸). Acta Cryst. C71, 9-18] procedure in PLATON. The solvent is included in the reported mol-ecular formula, weight and density.

trans-Chloridobis-(ethane-1,2-di-amine-κ(2) N,N')(thio-cyanato-κN)cobalt(III) diammine-tetra-kis-(thio-cyanato-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-di-amine) 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 mol-ecules into a three-dimentional supra-molecular network. Intensity statistic indicated twinning by non-mero-hedry with refined weighs of twin components are 0.5662:0.4338.

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 Fe(II) 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 octa-hedral coordination geometry. The Cu(I) ion is coordinated by two phenanthroline ligands in a distorted tetra-hedral 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 inter-actions are observed, with centroid-centroid distances in the range 3.512 (3)-3.859 (3) Å.

Hexa-kis-(dimethyl-formamide-κO)manganese(II) (dimethyl-formamide-κO)pentakis(-thio-cyanato--κN)chromate(III).

The title compound, [Mn(C(3)H(7)NO)(6)][Cr(NCS)(5)(C(3)H(7)NO)], 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-hy-droxy-eth-yl)tetra-zole 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 = dimethyl-formamide). The Mn(II) and Cr(III) atoms show a slightly distorted octa-hedral MnO(6) and CrN(5)O coordination geometries with adjacent angles in the range 85.29 (13)-95.96 (14)°.

Tris(1,10-phenanthroline-κ(2)N,N')iron(II) bis-[(1,10-phenanthroline-κ(2)N,N')tetra-kis-(thio-cyanato-κN)chromate(III)] acetonitrile tris-olvate monohydrate.

Single crystals of the title heterometallic compound, [Fe(C(12)H(8)N(2))(3)][Cr(NCS)(4)(C(12)H(8)N(2))](2)·3CH(3)CN·H(2)O or [Fe(Cphen)(3)][Cr(NCS)(4)(phen)](2)·3CH(3)CN·H(2)O, were pre-pared 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 mol-ecules and a water mol-ecule. The Fe and Cr atoms both show a slightly distorted octa-hedral FeN(6) and CrN(6) 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{µ(2)-2-[(2-hy-droxy-eth-yl)(meth-yl)amino]-ethano-lato}bis-(µ(3)-N-methyl-2,2'-aza-nediyldiethano-lato)tetra-kis-(thio-cyan-atato-κN)dichromium(III)dimanganese(II) dimethyl-formamide tetra-solvate.

The heterometallic title complex, [Cr(2)Mn(2)(C(5)H(11)NO(2))(2)(C(5)H(12)NO(2))(2)(NCS)(4)]·4C(3)H(7)NO, was prepared using manganese powder, Reineckes salt, ammonium thio-cyanate and a non-aqueous solution of N-methyl-diethano-lamine in air. The centrosymmetric mol-ecular structure of the complex is based on a tetra-nuclear {Mn(2)Cr(2)(µ-O)(6)} core. The tetra-nuclear complex mol-ecule and the two uncoordinated dimethyl-formamide mol-ecules are linked by O-H⋯O hydrogen bonds, while the two other mol-ecules of dimethyl-formamide do not participate in hydrogen bonding.

Diammine(2,2'-bipyridine)-bis(thio-cyan-ato--κN)cobalt(III) diamminetetra-kis(thio-cyanato--κN)chromate(III) aceto-nitrile disolvate.

The new heterometallic title complex, [Co(NCS)(2)(C(10)H(8)N(2))(NH(3))(2)][Cr(NCS)(4)(NH(3))(2)]·2CH(3)CN, 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)(NH(3))(2)(dpy)](+) and anionic [Cr(NCS)(4)(NH(3))(2)](-) building blocks, both with 2 symmetry, and acetonitrile solvent mol-ecules, which are linked together by N-H⋯N hydrogen bonds, forming extended supra-molecular chains. Furthermore, N-H⋯S, C-H⋯S and C-H⋯N hydrogen bonds inter-link neighbouring chains into a three-dimensional framework. The Co atom is in an elongated octa-hedral coordination environment with two N atoms from the dpy ligands and two NCS-groups in the equatorial plane and with two NH(3) mol-ecules at the axial positions. The Cr(III) ion is octa-hedraly coordinated by two NH(3) mol-ecules at the axial positions and four NCS-groups in the equatorial plane. Intensity statistics indicated non-merohedral twinning with the twin matrix [100; 0[Formula: see text]0; [Formula: see text]0[Formula: see text]]. The refined ratio of the twin components is 0.530 (1):0.470 (1).

Cr(III)-Cr(III) interactions in two alkoxo-bridged heterometallic Zn2Cr2 complexes self-assembled from zinc oxide, Reinecke's salt, and diethanolamine.

Two new tetranuclear complexes, [Zn(2)Cr(2)(NCS)(4)(Dea)(2)(HDea)(2)].4DMSO (1; DMSO = dimethyl sulfoxide) and [Zn(2)Cr(2)(NCS)(4)(Dea)(2)(HDea)(2)].2CH(3)CN (2), were prepared from zinc oxide, Reinecke's salt, NH(4)[Cr(NCS)(4)(NH(3))(2)].H(2)O, ammonium thiocyanate, and a nonaqueous solution of diethanolamine (H(2)Dea) in a reaction carried out under open air. Both compounds have similar centrosymmetric crystal structures based on a tetranuclear {Zn(2)Cr(2)(mu(3)-O)(2)(mu-O)(4)} core. Variable-temperature magnetic susceptibility measurements of 1 and 2 show weak antiferromagnetic coupling between chromium centers. The magnetic data and high-field, high-frequency electron paramagnetic resonance spectra were analyzed in terms of the spin Hamiltonian H = JS(1).S(2) - j(S(1).S(2) + mu(B)B{g(1)}S(1) + D(Cr){S(z1)(2) - S(1)(S(1) + 1)/3} + E(Cr)(S(x1)(2) - S(y1)(2)) + mu(B)B{g(2)}S(2) + D(Cr){S(z2)(2) - S(2)(S(2) + 1)/3} + E(Cr)(S(x2)(2) - S(y2)(2)) + D(12){S(z1)S(z2) - S(1).S(2)/3} + E(12)(S(x1)S(x2) - S(y1)S(y2)) with J = 13.7 cm(-1), j = 1.1 cm(-1), D(Cr) = 0.3864 cm(-1), E(Cr) = -0.1104 cm(-1), D(12) = -0.1873 cm(-1), and E(12) = -0.0155 cm(-1) for 1 and J = 9.4 cm(-1), j = 0.8 cm(-1), D(Cr) = 0.3564 cm(-1), E(Cr) = -0.0647 cm(-1), D(12) = -0.1850 cm(-1), and E(12) = -0.0112 cm(-1) for 2. Density functional theory (DFT) calculations were employed to calculate the zero-field splitting on Cr(3+) ions. Calculations of the exchange integrals J were attempted by using the "broken-symmetry" DFT method.

An extremely rare example of asymmetric tetranuclear core {M(4)(mu(3)-X)(2)(mu-X)(4)} in a novel alkoxo-bridged heterometallic Cr/Cd complex.

A novel heterometallic tetranuclear complex [Cr(3)Cd(NCS)(4)(H(2)tea)(Htea)(3)].3CH(3)OH () has been prepared using cadmium oxide, Reinecke's salt, ammonium thiocyanate and a methanol solution of triethanolamine (H(3)tea) in air. Crystallographic investigations reveal that the molecular structure of the complex is based on an uncommon asymmetric {Cr(3)Cd(mu(3)-O)(2)(mu-O)(4)} core with firstly observed terminal coordination of the NCS-groups in such molecular structure type. A network of O-HO hydrogen bonds as well as SS interactions link the molecules into a two-dimensional supramolecular network. Variable-temperature (1.8-300 K) magnetic susceptibility measurements show a change of the mu(B) value at low temperature, indicative of antiferromagnetic interactions (J = -7.45 cm(-1)) between chromium(iii) centers.

Direct synthesis of an heterometallic {Mn(II)3Cr(III)4} 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.