Impact of the anion and chalcogen on the crystal structure and properties of 4,6-dimethyl-2-pyrimido(thio)nium halides

By the reaction of urea or thiourea, acetylacetone and hydrogen halide (HF, HBr or HI), we have obtained seven new 4,6-dimethyl-2-pyrimido(thio)nium salts, which were characterized by single-crystal X-ray diffraction, namely, 4,6-dimethyl-2-oxo-2,3-dihydropyrimidin-1-ium bifluoride, C₆H₉N₂O⁺·HF₂⁻ or (dmpH)F₂H, 4,6-dimethyl-2-oxo-2,3-dihydropyrimidin-1-ium bromide, C₆H₉N₂O⁺·Br⁻ or (dmpH)Br, 4,6-dimethyl-2-oxo-2,3-dihydropyrimidin-1-ium iodide, C₆H₉N₂O⁺·I⁻ or (dmpH)I, 4,6-dimethyl-2-oxo-2,3-dihydropyrimidin-1-ium iodide–urea (1/1), C₆H₉N₂O⁺·I⁻·CH₄N₂O or (dmpH)I·ur, 4,6-dimethyl-2-sulfanylidene-2,3-dihydropyrimidin-1-ium bifluoride–thiourea (1/1), C₆H₉N₂S⁺·HF₂⁻·CH₄N₂S or (dmptH)F₂H·tu, 4,6-dimethyl-2-sulfanylidene-2,3-dihydropyrimidin-1-ium bromide, C₆H₉N₂S⁺·Br⁻ or (dmptH)Br, and 4,6-dimethyl-2-sulfanylidene-2,3-dihydropyrimidin-1-ium iodide, C₆H₉N₂S⁺·I⁻ or (dmptH)I. Three HCl derivatives were described previously in the literature, namely, 4,6-dimethyl-2-oxo-2,3-dihydropyrimidin-1-ium chloride, (dmpH)Cl, 4,6-dimethyl-2-sulfanylidene-2,3-dihydropyrimidin-1-ium chloride monohydrate, (dmptH)Cl·H₂O, and 4,6-dimethyl-2-sulfanylidene-2,3-dihydropyrimidin-1-ium chloride–thiourea (1/1), (dmptH)Cl·tu. Structural analysis shows that in 9 out of 10 of these compounds, the ions form one-dimensional chains or ribbons stabilized by hydrogen bonds. Only in one compound are parallel planes present. In all the structures, there are charge-assisted N⁺—H∙∙∙X⁻ hydrogen bonds, as well as weaker Cₐᵣ⁺—H∙∙∙X⁻ and π⁺∙∙∙X⁻ interactions. The structures can be divided into five types according to their hydrogen-bond patterns. All the compounds undergo thermal decomposition at relatively high temperatures (150–300°C) without melting. Four oxopyrimidinium salts containing a π⁺∙∙∙X⁻∙∙∙π⁺ sandwich-like structural motif exhibit luminescent properties.

Ion recognition properties of new pyridine-2,6-dicarboxamide bearing propeller-like pendant residues: multi-spectroscopic approach

The synthesis and ion binding properties of new amide derived from propeller-like tris(2-pyridyl)amine and 2,6-pyridinedicarboxylic acid chloride were described. Amide binds divalent metal cations: copper(II), nickel(II), zinc(II), and lead(II) in acetonitrile. In acetonitrile:water mixture (9:1 v/v) amide interacts only with copper(II) and nickel(II) cations forming complexes of 1:1 stoichiometry. It was found that the introduction of bulky, nitrogen donor atom bearing pendant groups can influence coordination mode of pyridine-2,6-dicarboxamides. The probable model of ligand-ion interactions is proposed on the basis of 1H NMR and FT-IR spectroscopy.

Photoresponsive, amide-based derivative of embonic acid for anion recognition

The synthesis and ion-binding properties of amide-based derivative of embonic acid andp-aminoazobenzenewere described. The new compound was characterized by X-ray structural analysis and spectroscopic methods.Ligand interacts in acetonitrile with Y-shaped anions (benzoates and acetates) and dihydrogen phosphatesforming complexes of 1:1 stoichiometry. In more polar DMSO the complexes stoichiometry changes to 2:1(L:anion). Light-inducedtranstocisisomerization was studied. The effect of anions on thermal back iso-merization was investigated.

Copper(I) iodide ribbons coordinated with thiourea derivatives

Two products of the reactions of CuI with 1-benzoyl-3-(4-bromophenyl)thiourea and with 1-benzoyl-3-(2-iodophenyl)thiourea have been obtained and characterized, namely poly[[[1-benzoyl-3-(4-bromophenyl)thiourea-κS]-µ3-iodidocopper(I)] acetone hemisolvate], {[CuI(C₁₄H₁₁BrN₂OS)]‧0.5C₃H₆O}ₙ, and poly-[µ₄-iodido-µ₃-iodido-[N-(benzo[d]thiazol-2-yl)benzamide-κN]dicopper(I)], [Cu₂I₂(C₁₄H₁₀N₂OS)]ₙ. Their structures, determined by single-crystal X-ray diffraction analysis, exhibit different stoichiometries and molecular organizations; however, both compounds are polymeric and possess close Cu‧‧‧Cu contacts. The first product contains a (CuI)ₙ double chain supported by the thiourea derivative coordinated via the S atom. In the second case, the ligand undergoes dehalogenation and cyclization to form N-(benzo[d]thiazol-2-yl)benzamide that serves as the N-donor ligand which is connected to both sides of a (CuI)ₙ quadruple chain. In both hybrid inorganic chains, I atoms bridge three or four Cu atoms. The coordination centres adopt more or less distorted tetrahedral geometries. The structures of the (CuI)ₙ kernels of the ribbons are similar to fragments of the layers in high-pressure phase V copper(I) iodide. Only weak S‧‧‧O, C—H‧‧‧O, C—H‧‧‧I and π–π interactions hold the ribbons together, allowing the formation of crystals.

Novel complexes possessing Hg–(Cl, Br, I)⋯O=C halogen bonding and unusual Hg₂S₂(Br/I)₄ kernel. The usefulness of τ₄′ structural parameter

One mononuclear and two binuclear Hg(II) complexes have been synthesized and characterized by X-ray diffraction, ATR IR and Hirshfeld surface analysis. Single-crystal X-ray diffraction showed that binuclear compounds are centrosymmetric and isostructural. All complexes form bifurcated intermolecular N–H···O hydrogen bonds that contribute to a formation of the centrosymmetric dimers. In binuclear complexes, sulfur atoms of thiourea ligands take the bridging role. These are the first examples of such compounds with mercury. In binuclear complexes of group 12 elements, halogens are usually the bridging atoms. The geometries of binuclear complexes are highly distorted with alarmingly low value of τ₄' parameter suggesting presence of additional donor that turned out to be phenyl ring (Hg···π interaction). The crystal structures are stabilized by additional noncovalent interactions, including halogen bonding which leads to the formation of chains. The differences and similarities of these complexes indicate that halogen ions have a great impact on the structures. Presented complexes comprise unique interactions between mercury-bonded halogen atoms and neighboring oxygen atoms of carbonyl groups (Hg–(Cl,Br, I)···O=C contacts).

Crystallographic study of self-organization in the solid state including quasi-aromatic pseudo-ring stacking interactions in 1-benzoyl-3-(3,4-dimethoxyphenyl)thiourea and 1-benzoyl-3-(2-hydroxypropyl)thiourea

1-Benzoylthioureas contain both carbonyl and thiocarbonyl functional groups and are of interest for their biological activity, metal coordination ability and involvement in hydrogen-bond formation. Two novel 1-benzoylthiourea derivatives, namely 1-benzoyl-3-(3,4-dimethoxyphenyl)thiourea, C₁₆H₁₆N₂O₃S, (I), and 1-benzoyl-3-(2-hydroxypropyl)thiourea, C₁₁H₁₄N₂O₂S, (II), have been synthesized and characterized. Compound (I) crystallizes in the space group P1̅, while (II) crystallizes in the space group P2₁/c. In both structures, intramolecular N-H···O hydrogen bonding is present. The resulting six-membered pseudo-rings are quasi-aromatic and, in each case, interact with phenyl rings via stacking-type inter­actions. C−H···O, C−H···S and C−H···π interactions are also present. In (I), there is one molecule in the asymmetric unit. Pairs of molecules are connected via two intermolecular N-H···S hydrogen bonds, forming centrosymmetric dimers. In (II), there are two symmetry-independent molecules that differ mainly in the relative orientations of the phenyl rings with respect to the thiourea cores. Additional strong hydrogen-bond donor and acceptor -OH groups participate in the formation of inter­molecular N−H···O and O−H···S hydrogen bonds that join molecules into chains extending in the [001] direction.

Coordination polymers and molecular structures among complexes of mercury(II) halides with selected 1-benzoylthioureas

Six new 1-benzoyl-3-phenylthiourea and 1-benzoyl-3-(2-methylphenyl)thiourea complexes of mercury( II) were obtained in the reactions of the ligands with HgX2 in methanol (X = Cl, Br, I). Their structures, determined by single-crystal X-ray diffraction analysis, exhibit different stoichiometries and molecular organization. Coordination centers adopt more or less distorted tetrahedral geometry (five structures) or distorted trigonal bipyramidal geometry (one structure). In four cases 1D coordination polymers were formed and in the other two molecular compounds were found. In three cases solvent molecules (H2O or MeOH) were found in crystal structure. Although all compounds share common intramolecular N–H...O=C structural motif they exhibit unique hydrogen bonding pattern. Common pc11 rod group symmetry of polymer chains (where applicable) allows simplified classification of the 3D packing as parallel stacking of trapezoidal prisms

Synteza i badania strukturalne związków kompleksowych miedzi(I) i rtęci(II) z wybranymi ligandami tioamidowymi

A. Okuniewski – 2015
Przedstawiona rozprawa doktorska poświęcona jest związkom tiokarbonylowym (wybranym tioamidom i tiomocznikom) oraz ich połączeniom kompleksowym z halogenkami miedzi(I) i rtęci(II). Istota i cel takich badań przedstawione są we wstępie pracy. W części teoretycznej opisane zostały kluczowe pierwiastki wchodzące w skład syntezowanych związków kompleksowych (siarka, miedź i rtęć), jak również tioamidy i tiomoczniki. Szczególna uwaga została poświęcona 1-acylotiomocznikom. W dalszej części znajdują się podstawowe informacje dotyczące związków kompleksowych, krystalografii oraz stosowanych parametrów liczbowych. Na początku części eksperymentalnej przedstawione zostały zastosowane techniki badawcze oraz obliczeniowe. Następnie opisane zostały substraty do syntez oraz same syntezy. Część zastosowanych ligandów dostępna jest handlowo, jednak zdecydowana większość z nich była syntezowana w ramach prowadzonych badań. W niektórych przypadkach wyizolowano nieoczekiwane produkty oksydacyjnej heterocyklizacji. Wszystkie otrzymane związki, które udało się scharakteryzować opisane zostały w rozdziale Wyniki i dyskusja. Wnioski zebrane zostały w odrębnym rozdziale. Dotyczą one geometrii centrów koordynacji oraz samych ligandów, porównania polimerów koordynacyjnych oraz związków izostrukturalnych. Pracę kończą dodatki, wśród których znajdują się tabele z wartościami liczbowymi, opisy działania algorytmów autorskich programów LattE i Ortho, a także bibliografia. Do pracy dołączona jest rozkładana strona z zestawieniem omawianych związków oraz płyta CD.

Bis(diisopropylammonium) thiosulfate and bis(tert-butylammonium) thiosulfate

Two new dialkylammonium thiosulfates, namely bis(diisopropylammonium) thiosulfate, 2C6H16N+S2O3 2-, (I), and bis(tert-butylammonium) thiosulfate, 2C4H12N+S2O3 2-, (II), have been characterized. The secondary ammonium salt (I) crystallizes with Z = 4, while the primary ammonium salt (II), with more hydrogen-bond donors, crystallizes with Z = 8 and a noncrystallographic centre of inversion. In both salts, the organic cations and thiosulfate anions are linked within extensive N—H...O and N—H...S hydrogen-bond networks, forming extended two-dimensional layers. Layers are parallel to (101) in (I) and to (002) in (II), and have a polar interior and a nonpolar hydrocarbon exterior. The layered structure and hydrogen-bond motifs observed in (I) and (II) are similar to those in related ammonium sulfates.


In the title compound, C32H30N4O2S2, the carbonyl and thiocarbonyl groups are found in a rare synclinal conformation, with an S-C···C-O pseudo-torsion angle of 62.6(2)°. The molecule has Ci = S2 point-group symmetry with a crystallographic center of inversion located in the middle of the ethylene bridge. One of the symmetry-independent phenyl rings is disordered over two orientations, with a site-occupation ratio of 70:30. The distances between the centroids of the nearest phenyl rings are equal to one of the lattice constants [a = 4.7767(2) Å], so stacking interactions are extremely weak. Molecules are joined by bifurcated hydrogen bonds (N-H···O and N-H···S), forming a ladder-like arrangement along [100]. van der Waals forces combine these ladders into a three-dimensional structure. The dependency between the S···O distance and the improper S=C···C=O torsion angle based on 739 structures containing the CC(=O)NC(=S)N moiety is discussed.