The honeycomb network structure of poly[[[μ2‐1,3‐bis(1H‐benzimidazol‐2‐yl)benzene‐κ2N3:N3′](μ2‐terephthalato‐κ2O:O′)zinc(II)] ethanol solvate]

The terephthalate dianion and the bis(imidazolyl)benzene ligand of the title compound, {[Zn(C₈H₄O₄)(C₂₀H₁₄N₄)]·C₂H₆O}_n, each bridges two adjacent zinc centers, resulting in a layer‐type coordination polymer; the zinc center shows tetrahedral coordination. The disordered ethanol solvent molecules occupy the spaces between the layers and are hydrogen bonded to the layers. The two symmetry‐independent dianions lie on different inversion sites.     

Bis[bis­(methoxy­carbimido)amine‐κ2N,N′]bis­(perchlorato‐κO)copper(II) bis­[bis­(methoxy­carbimido)amine‐κ2N,N′]bis­(methanol‐κO)copper(II) bis­(perchlorate) methanol disolvate

The title compound, [Cu(ClO₄)₂(C₄H₉N₃O₂)₂][Cu(C₄H₉N₃O₂)₂(CH₄O)₂](ClO₄)₂·2CH₃OH, comprises two independent Cu^II species lying on different inversion sites. In the Cu complexes, a distorted octa­hedral geometry arises (from basic square‐planar N₄ coordination) from the weak coordination of two perchlorate ions (as Cu—O) in one species and two methanol mol­ecules in the other (also as Cu—O). Inter­actions between the O atoms of the perchlorate anions or methanol groups and the imide or amine NH groups afford an extensive inter­molecular hydrogen‐bonding network.     

Tetra‐μ‐acetato‐κ2O:O′‐bis[(4‐phenylpyridine‐κN)copper(II)]

The title compound, [Cu₂(C₂H₃O₂)₄(C₁₁H₉N)₂] or [Cu₂(MeCO₂)₄(phpy)₂] (phpy is 4‐phenyl­pyridine), consists of centrosymmetric dimers in which the Cu^II atoms display a square‐pyramidal CuO₄N coordination, with four acetate O atoms in the basal plane [Cu—O 1.975 (3)–1.987 (3) Å] and the phpy N atom in the apical position [Cu—N 2.150 (3) Å]. The Cu atoms are 2.654 (1) Å apart and are bridged by four acetate groups. The discrete dimers are extended into a three‐dimensional supramolecular array through intermolecular π–π‐stacking interactions.     

Ru-catalyzed synthesis of substituted phthalides through C–H bond activation and functionalization

Synthesis of substituted phthalides through a ruthenium-catalyzed reaction of phthalic anhydrides with acrylates is described. The reaction proceeds via CH bond activation and leads to the formation of vinylated phthalides through a successive double vinylation accompanied by decarboxylation and annulation reactions.     

The synthesis and reactivity of polysilylacetylenes: Diels—Alder reactions to give bis (silyl) benzenes

Six bis(silyl)acetylenes (XMe²Si? C?C? SiMe₂X) with the following varied silicon substituents X were prepared: 1 (Me, Me); 2 (H, H); 3 (C1, H); 4 (CI, CI); 5 (MeO, H); 6 (MeO, MeO). While 1 and 2 may be prepared by the reaction of dilithio- or bis(bromomagnesium)-acetylide with the appropriate chlorosilane, similar reactions designed to give 3–6 yielded oligomers, XMe₂Si? (? C?C? SiMe₂)_n? X, 7, X=CI, MeO, as the major products, indicating that the acetylenic functionality on silicon activates the chlorosilane towards nucleophilic substitution. Compounds 3 and 4 were prepared by free radical chlorination of 2. Methanolysis of 3 and 4 gave quantitative yields of 5 and 6 respectively. Compounds 1–6 undergo a Diels–Alder reaction with α-pyrone to produce, after loss of carbon dioxide, bis(silyl)-substituted benzene derivatives. The order of reactivity has been determined to be: 4=6>3=5>1>2, indicating that chloro or alkoxy substituents favor the cycloaddition with 2- pyrone. The adducts formed by compounds 3–6 undergo an unusually facile hydrolysis or elimination to give 1,1,3,3-tetramethyl-1,3-disila-2-oxaindane.     

2-（1,3-Diphenylpropen-1,3-diolato）-1,3,2-（5-formylbenzo）dioxaborol： A ＇Whole-molecule Disorder＇ Crystal Structure

The boron atom in C22H15BO5 is O,O’-chelated by the anions in a tetrahedral geometry, with the planar five-and six-membered chelate rings being orthogonal to each other. The molecule lies on a two-fold rotation axis. The molecule is disordered with respect to another molecule in a 93:7 ratio; the treatment of the ‘whole-molecule disorder’ by employing a large number of restraints is described. Crystal data: C22H15BO5, monoclinic C2/c, a = 17.1804(5), b = 12.9409(4), c = 9.8842(3) , β = 124.832(2)o, V = 1803.82(9) 3 at –173 K.     

Syntheses,Structural Characterization and Thermoanalysis of Transition-Metal Compounds Derived from 3,5-Dinitropyridone

Abstract  

Nine metal compounds of Mn(II), Zn(II) and Cd(II) derived from dinitropyridone ligands (3,5-dinitropyrid-2-one, 2HDNP; 3,5-dinitropyrid-4-one, 4HDNP and 3,5-dinitropyrid-4-one-N- hydroxide, 4HDNPO) were characterized by elemental analysis, FT-IR and partly by TG-DSC. Three of which were further structurally characterized by X-ray single-crystal diffraction analysis. The structures of the three compounds, Mn(4DNP)₂(H₂O)₄, 4, Zn(4DNPO)₂(H₂O)₄, 8, and Cd(4DNPO)₂(H₂O)₄, 9, crystallize in the monoclinic space group P2(1)/n and Z = 2, with a = 8.9281(9), b = 9.1053(9), c = 10.6881(11) Å, β = 97.9840(10)° for 4; a = 8.4154(7), b = 9.9806(8), c = 10.5695(8) Å, β = 97.3500(10)° for 8; a = 8.5072(7), b = 10.2254(8), c = 10.5075(8) Å, β = 96.6500(10)° for 9. All three complexes are octahedral consisting of four equatorial water molecules, and two nitrogen or oxygen donor ligands (DNP or DNPO). The abundant hydrogen-bonding and π-π stacking interactions seem to contribute to stabilization of the crystal structures of the compounds. The TG-DTG results revealed that the complexes showed a weight loss sequence corresponding to all coordinated water molecules, nitro groups, the breaking of the pyridine rings and finally the formation of metal oxides.     

catena‐Poly­[[[bis­(perchlorato‐O)­(1,10‐phenanthroline‐N,N′)­copper(II)]‐μ‐4,4′‐bi­pyridine‐N:N′] monohydrate]

The Cu atom in the title complex {[Cu(C₁₀H₈N₂)(C₁₂H₈N₂)(ClO₄)₂]·H₂O}_n, has an N₄O₂ octahedral coordination geometry, the Cu atoms being bridged by the bi­pyridine and chelated by the phenanthroline heterocycles. Adjacent mol­ecules are linked into a zigzag chain running along the c axis of the monoclinic unit cell. The chains are connected through lattice water mol­ecules to produce a layer structure.     

Crystallographic report: Crystal structure of a two‐dimensional coordination polymer: tetraaqua‐1,2,4,5‐benzenetetracarboxylato(pyrazine)dizinc(II) dihydrate

The structure of {[Zn₂(1,2,4,5‐btc)(pz)(H₂O)₄]·2(H₂O)}_n (1,2,4,5‐btc = 1, 2, 4, 5‐benzenetetracarboxylate, pz = pyrazine) is a two‐dimensional coordination network. The zinc(II) center is in a distorted octahedral NO₅ coordination environment that is defined by one nitrogen atom of pyrazine, three oxygen atoms of carboxyl groups from 1,2,4,5‐benzenetetracarboxylate tetraanions and two water molecules. Copyright © 2003 John Wiley & Sons, Ltd.