A Proton Complex of p-tert-Butylcalix[4]arene-tetrakis(N,N-dimethylthioacetamide): NMR Evidence and Probable Structure

Using ¹H and ¹³C NMR together with density functional theoretical (DFT) calculations, it is shown that p-tert-butylcalix[4]arene-tetrakis(N,N-dimethylthioacetamide) (1) forms a stable equimolecular complex with proton in the form of hydroxonium ion in nitrobenzene-d ₅. Protons were offered by hydrogen bis(1,2-dicarbollyl) cobaltate (HDCC) and converted to hydroxonium ions by traces of water. The complex 1·H₃O⁺ adopts a slightly asymmetric but rapidly motionally averaged conformation, which is distinctly more cone-like than ligand 1. The hydroxonium ion H₃O⁺ is bound partly to thiocarbonyl sulphur atoms and partly to phenoxy oxygen atoms of 1 by strong hydrogen bonds and other electrostatic interactions.

     

Zoledronate complexes. I. Poly[[μ2‐aqua[μ3‐1‐hydroxy‐2‐(1H,3H‐imidazol‐3‐ium‐1‐yl)ethylidenediphosphonato]potassium(I)] monohydrate]

The title compound, {[K(C₅H₉N₂O₇P₂)(H₂O)]·H₂O}_n, is polymeric and consists of layers parallel to (001) interconnected by hydrogen‐bonding and π–π interactions. The K⁺ cation is eightfold coordinated in a KO₈ environment by O atoms from three different chelating zoledronate units and two coordinated water molecules. The zoledronate group presents its usual zwitterionic character, with negative charges in the singly protonated phosphonate groups and a positive charge at the protonated imidazole N atom. The anion binds to three different K⁺ cations in a (so far unreported) triply chelating manner. Intra‐ and interplanar interactions are enhanced by a variety of hydrogen bonds involving all available O—H and N—H donors. A strong imidazole–phosphonate C—H...O interaction is present in the structure.     

Adducts of 1,1,1‐tris(4‐hydroxyphenyl)ethane with diamines: three‐dimensional hydrogen‐bonded frameworks formed with 1,6‐diaminohexane and 2,2′‐bipyridyl

The adduct 1,6‐di­amino­hexane–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2) is a salt {hexane‐1,6‐diyldiammonium–4‐[1,1‐bis(4‐hydroxyphenyl)ethyl]phenolate (1/2)}, C₆H₁₈N₂²⁺·2C₂₀H₁₇O₃^?, in which the cation lies across a centre of inversion in space group P. The anions are linked by two short O—H?O hydrogen bonds [H?O 1.74 and 1.76 Å, O?O 2.5702 (12) and 2.5855 (12) Å, and O—H?O 168 and 169°] into a chain containing two types of R(24) ring. Each cation is linked to four different anion chains by three N—H?O hydrogen bonds [H?O 1.76–2.06 Å, N?O 2.6749 (14)–2.9159 (14) Å and N—H?O 156–172°]. In the adduct 2,2′‐bipyridyl–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2), C₁₀H₈N₂·2C₂₀H₁₈O₃, the neutral di­amine lies across a centre of inversion in space group P2₁/n. The tris­(phenol) mol­ecules are linked by two O—H?O hydrogen bonds [H?O both 1.90 Å, O?O 2.7303 (14) and 2.7415 (15) Å, and O—H?O 173 and 176°] into sheets built from R(38) rings. Pairs of tris­(phenol) sheets are linked via the di­amine by means of a single O—H?N hydrogen bond [H?N 1.97 Å, O?N 2.7833 (16) Å and O—H?N 163°].     

An unusual two‐dimensional hydrogen‐bonding network in bis(2,9‐dimethyl‐1,10‐phenanthrolin‐1‐ium) peroxodisulfate dihydrate

The title compound, 2C₁₄H₁₃N₂⁺·S₂O₈²⁻·2H₂O, is a protonated amine salt which is formed from two rather uncommon ionic species, namely a peroxodisulfate (pds²⁻) anion, which lies across a crystallographic inversion centre, and a 2,9‐dimethyl‐1,10‐phenanthrolin‐1‐ium (Hdmph⁺) cation lying in a general position. Each pds²⁻ anion binds to two water molecules through strong water–peroxo O—H...O interactions, giving rise to an unprecedented planar network of hydrogen‐bonded macrocycles which run parallel to (100). The atoms of the large R₈⁸(30) rings are provided by four water molecules bridging in fully extended form (...H—O—H...) and four pds²⁻ anions alternately acting as long (...O—S—O—O—S—O...) and short (...O—S—O...) bridges. The Hdmph⁺ cations, in turn, bind to these units through hydrogen bonds involving their protonated N atoms. In addition, the crystal structure also contains π–π and aromatic–peroxo C—H...O interactions.