Octakis(ɛ‐caprolactam‐κO)erbium(III) hexaisothiocyanatochromate(III)

The title compound, [Er(C₆H₁₁NO)₈][Cr(NCS)₆], is a new structure type for [Ln(ɛ‐caprolactam)₈][Cr(NCS)₆], where Ln is a lanthanide. There are two independent cations and two independent anions in the asymmetric unit. The Er atom is in a distorted square‐antiprismatic environment of eight O atoms of the organic ligands; Er—O bond distances are in the range 2.29–2.44 Å. The coordination environment of the Cr atom is a slightly distorted octahedron; Cr—N bond distances vary from 1.99 to 2.01 Å. The mutual packing of the cations and the anions follows a distorted NaCl motif. One cation has the Er atom on a twofold axis and one of the anions has the Cr atom on a twofold axis.     

Synthesis, Formation Mechanism, and Crystal Structure of the Nitrosoruthenium(II) Nitrochloride Complex Fac-K2[RuNO(NO2)2Cl3]

Procedures for synthesis of the first nitrochloride complex of nitrosoruthenium(II), fac-K₂[RuNO(NO₂)₂Cl₃], are described and the mechanism of its formation is suggested. The compound was investigated by IR spectroscopy and X-ray phase and X-ray diffraction analyses. Crystal data for Cl₃N₃O₅K₂Ru: a = 7.050(1), b = 7.524(2), c = 10.125(2) , = 90.44(3), = 103.17(3), = 90.51(3)°, V = 522.9 ³, space group , Z = 2, d _calc = 2.589 g/cm³. The structure consists of the complex anions fac-[RuNO(NO₂)₂Cl₃]^2– and K⁺ cations. The complex crystallizes as triclinic plates and red orange prisms; it is well soluble in water, not readily soluble in KCl solutions, and insoluble in ethanol and acetone; the complex is stable when stored in air.     

Synthesis and structure of a new octahedral molybdenum thiocyanide cluster complex K7[Mo6(μ3-S)8(CN)6]·8H2O

The new octahedral molybdenum thiocyanide cluster complex K₇[Mo₆S₈(CN)₆]·8H₂O was synthesized by excision of the cluster core (the reaction of ZnMo₆S₈ with a melt of KCN). The structure of the complex was established by X-ray diffraction analysis. The reaction of Mo₆Se₈ with a KCN—KSCN mixture afforded the mixed-ligand cluster anions [Mo₆(Se,S)₈(CN)₆]^7–. The salt of composition K_1.5Cs_5.5[Mo₆Se_6.8S_1.2(CN)₆]·8H₂O was obtained. The complexes are isostructural to each other and to the selenium analog described previously. The magnetic properties and the electronic and IR spectra were measured and discussed.     

Crystal Structure of the Ca2+ Supramolecular Complex with Cucurbituryl {[Ca(H2O)3(HSO4)(CH3OH)]2(C36N24O12H36)}(HSO4)2 · 4H2O

The calcium(II) supramolecular complex with cucurbituryl of composition {[Ca(H₂O)₃(HSO₄)(CH₃OH)]₂(C₃₆N₂₄O₁₂H₃₆)}(HSO₄)₂ · 4H₂O is obtained by slow diffusion of methanol into a calcium(II) solution in 2 M H₂SO₄; its crystal structure is determined by X-ray diffraction analysis. The crystals are triclinic, a = 10.4030(9) Å, b = 11.936(1) Å, c = 15.119(1) Å, = 69.829(6)°, = 72.019(5)°, = 70.171(7)°, V = 1618.1(2) ų, space group P , Z = 1, _calcd = 1.754 g/cm³. The crystal structure is a pseudohexagonal packing of {[Ca(H₂O)₃(HSO₄)(CH₃OH)]₂(C₃₆N₂₄O₁₂H₃₆)}²⁺ cylinders shifted by half translation along the a axis. The cylinders are linked via hydrogen bonds, with the crystallization water molecules and HSO^– ₄ anions arranged in the channels.     

Chalcogen arsenide clusters of iron with a functional carboxyl group: Synthesis, structures, and thermolysis

The carbonyl clusters [Fe₃(??₃-Q)(??₃-AsR)(CO)₉] (Q = Se and Te; R = meta- and para-HOOCC₆H₄) were obtained from the salts K₂[Fe₃(??₃-Q)(CO)₉] and organoarsenic diiodides RAsI₂ prepared by reducing iodination of arsonic acids RAsO(OH)₂ according to a novel method. The structures of the clusters were identified by X-ray diffraction. The crystal packing motifs of the dimers of the cluster molecules and their relationship with the solubility of the clusters are discussed. The sequential steps of the thermolysis (decarbonylation, decarboxylation, and decomposition of the organic fragment) of the clusters were studied. The presence and location of the carboxyl group does not influence the decarbonylation temperature.     

Synthesis,structure, and luminescence of the octahedral molybdenum cluster [Mo6I8(SC6F4H)6]2−

A new thiolate cluster complex (Bu₄N)₂[Mo₆I₈(SC₆F₄H)₆] was synthesized by the metathesis reaction of (Bu₄N)₂[Mo₆I₁₄] and HC₆F₄SAg in methylene chloride. According to the X-ray structure determination, the cluster core {Mo₆I₈}⁴⁺ coordinates six thiolate ligands 2,3,5,6-HC₆F₄S^?. The Mo-Mo and Mo-I distances have their usual values. The average Mo-S distance is 2.538(4) Å, and the Mo-S-C angles range from 107 to 109°. Compound (Bu₄N)₂[Mo₆I₈(SC₆F₄H)₆] both in solid and in solution displays a bright red microsecond luminescence, which is typical of octahedral molybdenum halide complexes.     

Syntheses and structures of the cobalt, nickel, and zinc complexes with 1,4-diaza-1,3-butadiene ligands

Several cobalt(II), nickel(II), and zinc(II) complexes with a series of ligands of the 1,4-diaza-1,3-butadiene type bearing aryl (2,6-di-iso-propylphenyl, mesityl) and alkyl (tert-butyl, iso-propyl) substituents at the nitrogen atoms are synthesized. The obtained complexes are characterized by X-ray structure analysis, IR spectroscopy, and elemental analysis.     

Telluride clusters of molybdenum: Synthesis, structures, and NMR spectra

High-temperature reactions of Mo, chalcogen (S or Se), Te, and Br₂ in molar ratio Mo: S/Se: Te: Br = 3: 1: 6: 4 were carried out. The reaction products were subjected to mechanochemical activation with K(Dtp) (Dtp = (EtO)₂PS₂) in a vibrational mill, resulting in the formation of new compounds [Mo₃(μ₃-Q)_0.5(μ₃-O)_0.5(μ₂-Te₂)₃(Dtp)₃](Dtp) (Q = Se (I) and S (II)). The structure of compound I has been established by X-ray diffraction analysis. Solutions of compounds I and II contain mixtures of [Mo₃(μ₃-Q)(μ₂-Te₂)₃(Dtp)₃]⁺ and [Mo₃(μ₃-O)(μ₂-Te₂)₃(Dtp)₃]⁺, which is confirmed by mass spectrometry and ³¹P, ⁷⁷Se, and ¹²⁵Te NMR spectroscopy. Quantum-chemical calculations of the ¹²⁵Te NMR chemical shifts were performed. The compounds are also characterized by IR spectroscopy, Raman spectroscopy, and elemental analysis. Structure I contains short nonvalent contacts between the sulfur atom of the out-of-sphere Dtp anion and the axial tellurium atoms of the cluster.