A three‐dimensional framework of bis­[tris­(ethyl­enediamine)zinc] tetra­iodo­cadmate diiodide assisted by N—H⋯I hydrogen bonds

The title salt, [Zn(C₂N₂H₈)₃]₂[CdI₄]I₂, conventionally abbreviated [Zn(en)₃]₂[CdI₄]I₂, where en is ethyl­enediamine, contains discrete [Zn(en)₃]²⁺ cations and [CdI₄]²⁻ anions with distorted octa­hedral and nearly tetra­hedral geometries, respectively, as well as uncoordinated I⁻ ions. The cation and the free I⁻ anion lie on twofold rotation axes and the [CdI₄]²⁻ anion lies on a axis in the space group I2d. The structure exhibits numerous weak inter‐ionic hydrogen bonds of two types, viz. N—H⋯I⁻(free ion) and N—H⋯I([CdI₄]²⁻), which support the resulting three‐dimensional framework.     

New Luminescent Lanthanide Tetrakis-Complexes NEt4[LnL4] Based on Dimethyl-N-Benzoylamidophosphate

New lanthanide dimethyl-N-benzoylamidophosphate (HL) based tetrakis-complexes NEt₄[LnL₄] (Ln³⁺=La, Nd, Sm, Eu, Gd, Tb, Dy) are reported. The complexes are characterized by means of NMR, IR, absorption, and luminescent spectroscopy as well as by elemental, X-Ray, and thermal gravimetric analyses. The phenyl groups of the four ligands of the complex anion are directed towards one side, while the methoxy groups are directed in the opposite side, which makes the complexes under consideration structurally similar to calixarenes. The effect of changing the alkali metal counterion to the organic cation NEt₄⁺ on the structure and properties of the tetrakis-complex [LnL4]^- is analyzed. The complexes exhibit bright characteristic for respective lanthanides luminescence. Rather high intensity of the band of ⁵D₀→⁷F₄ transition, observed in the luminescence spectrum of NEt₄[EuL₄], is discussed based on theoretical calculations.     

The C-Cl···π interactions inside supramolecular nanotubes of hexaethynylhexamethoxy[6]pericyclyne

Model complexes of hexaethynylhexamethoxy[6]pericyclyne (HM6P) molecules, with or without dichloromethane (DCM) guests, have been calculated at the M05-2X/6-311G(d,p) DFT level. Analysis of nonbonding interactions shows that the cohesion of the supramolecular tubular assemblies previously observed in the crystal state, relies mainly on C-H···O hydrogen bonds between axial ethynyl and equatorial methoxy substituents of stacked HM6P C(18) macrocycles in a cyclohexane-like chair conformation. The intrinsic binding energy of one HM6P molecule with two neighbors is calculated to be more than 40 kcal mol(-1). The inner channel of the stacks (of ca. 8 ? diameter) are suitable for hosting DCM molecules. Using the Atoms In Molecules (AIM) theory, the interaction between DCM molecules and surrounding triple bonds is analyzed in terms of σ-hole-directed C-Cl···π halogen bonds. A σ-hole-directed Cl···Cl interaction between two chlorine atoms of different DCM molecules is also evidenced.     

Synthesis and Structure of Different-Metal Different-Ligand Germanium(IV) and Cobalt(II) or Copper(II) Complexes with 1-Hydroxyethylidenediphosphonic Acid and 1,10-Phenanthroline

Different-metal different-ligand complexes [{Co(Phen)₃}₂{Co(Phen)(H₂O)₄}₂][{Ge(μ-OH)(μ- Hedp)}₆Cl₂] (I), [{Cu(Phen)₂(H₂O)}₂(HPhen)₂][Ge(μ-OH)(μ-Hedp)]₆ · 20H₂O (II) (H₄Hedp = 1-hydroxyethylidenediphosphonic acid, Phen = 1,10-phenanthroline) were synthesized and studied by X-ray diffraction. According to X-ray diffraction data (CIF files CCDC nos. 1573112 (I), 1573113 (II)), compounds I and II are cation–anion type complexes in which the anions are represented by {[Ge(μ-OH)(μ-Hedp)]⁶}^6– and, in the case of I, two additional Cl^– ions, while the cations are [Co(Phen)₃]²⁺, [Co(Phen)(H₂O)₄]²⁺ in I and [Cu(Phen)₂(H₂O)]²⁺, HPhen⁺ in II. In the crystals of compounds I and II, the cations, anions, and water molecules are combined by numerous intermolecular hydrogen bonds, giving rise to a 3D network.     

N,N-Dimethylethylenediamine in direct and direct template syntheses of Cu(II)/Cr(III) complexes

Four new heterometallic Cu(II)/Cr(III) complexes with N,N-dimethylethylenediamine (dmen) and its novel Schiff-base derivatives, N′-[(1Z)-3-amino-1,3-dimethylbutylidene]-N,N-dimethylethane-1,2-diamine (dmenac) and N′-((1Z)-3-{[2-(dimethylamino)ethyl]amino}-1,3-dimethylbutylidene)-N,N-dimethylethane-1,2-diamine (dmen₂ac), have been easily prepared by self-assembly and characterized by spectroscopic methods and single crystal X-ray analysis. The structures of all the complexes are assisted by numerous hydrogen bonds that provide a web of interactions and mould the supramolecular architectures of the compounds. Variable-temperature (1.8–300 K) magnetic susceptibility measurements reveal Curie-Weiss paramagnetic behavior of all the compounds, supported by EPR studies.     

New carbacylamidophosphates (CAPh) and CAPh-containing coordination compounds: structural peculiarities

Structural Chemistry - The new carbacylamidophosphate derivative HL1 (1) with general formula Cl3CC(O)N(H)P(O)(CH2C5H4N)2 named...     

Expected and unforeseen reactions of 2,3,3-trimethyl-1λ6-isothiazolidine-1,1,4-trione and their spiro derivative

Herein, we present a full account of our studies with respect to the reactivity of insufficiently explored 1λ⁶-isothiazolidine-1,1,4-triones (so-called β-keto-γ-sultams). This heterocyclic system possesses two reaction centers: the EWG-activated methylene group and the carbonyl moiety which were investigated in the course of present study. 2,3,3-Trimethyl-1λ⁶-isothiazolidine-1,1,4-trione and 4-methyl-5λ⁶-thia-4-azaspiro[2.4]heptane-5,5,7-trione were chosen as representatives of the given class of substances. The former is a classical spatially uncomplicated model substance, the latter bearing a spiranic cyclopropane substituent is interesting in terms of evaluation of strain cycle effects. Indeed, the data obtained convey information about the impact of the highly strained substituent on the reaction centers of the ketosultam core. Thus, in addition to less stability of the strained spiranic ketosultam, the reactivity of its carbonyl group is suppressed whereas the activity of the methylene group is enhanced being compared with the nonspiranic substrate. Apart from the difference in the chemical character of the given β-keto-γ-sultams we faced unprecedented products (1,1-dioxo-5-[2-(triphenylphosphonio)acetyl]-2,3-dihydro-1H-1λ⁶-isothiazol-4-olates) formed during the course of the reaction with the Wittig reagent triphenylcarbethoxymethylenephosphorane.     

Synthesis and study of the structure of new 3d-metal coordination compounds with substituted 2-amino-4(5H)-ketothiophens

A series of new 3d-metal complexes based on 2-amino-3-(1-methylbenzimidazol-2-yl)-4(5H)-ketothiophen (HL¹) and 2-amino-3-(2-benzothiazolyl)-4(5H)-ketothiophen (HL²) were synthesized. Compounds of the general formulas [ML₂] and [M(HL¹)₂Cl₂] (where M = Co²⁺, Ni²⁺, Zn²⁺, Cu²⁺) were prepared by the reaction of the above mentioned ligands with the corresponding acetate (for [ML₂]) or chloride (for [M(HL¹)₂Cl₂]) salts in a methanol or a methanol–chloroform medium. The choice of the anion in the initial metal salt, as well as the selection of the ligand, is crucial for obtaining coordination compounds with a neutral or deprotonated form of the 2-amino-4(5H)-ketothiophens. Thus, in contrast to HL¹, complexes with the neutral form of HL² cannot be obtained under the same conditions. All the complexes were studied by spectroscopic methods and X-ray crystallography (for [CuL¹₂] · H₂O). The coordination polyhedron of the copper atom is formed by four nitrogen atoms from two ligand anions and the geometry of the coordination sphere is intermediate between tetrahedral and square-planar.     

Coordination compounds based on CAPh type ligand: synthesis,structural characteristics and luminescence properties of tetrakis-complexes CsLnL4 with dimethylbenzoylamidophosphate

Searching for prospective luminescent materials, the series of new lanthanide coordination compounds CsLnL₄ (Ln = La, Pr, Nd, Sm – Er, and Yb; L^? = {C₆H₅CONPO(OCH₃)₂}^-) was synthesized. X-ray diffraction studies of CsNdL₄ and CsYbL₄ have been performed establishing polymeric structures of the tetrakis-complexes built from [LnL₄]^? anions and cesium cations functioning as linkers. The IR, absorption, emission, excitation spectra, and decay time measurements at 298 and 77 K, as well as thermal gravimetric analyses, were used to characterize the complexes.     

Synthesis of new 7-alkylmethylene derivatives of 2-(thio)oxo-2,5,6,7-tetrahydro-1<Emphasis Type="Italic">H</Emphasis>-pyridine-3-carbonitriles

Alkylmethyleneamines of cyclic ketones were used for the synthesis of earlier unknown 7-alkylmethylene-2-(thio)oxo-2,5,6,7-tetrahydro-1H-pyridine-3-carbonitriles.