Fluorenonophane chlorobenzene solvate: molecular and crystal structures

The title compound, 19 H,79 H-3,5,9,11-tetraoxa-1,7(2,7)-difluorena-4,10(1,3)-dibenzenacyclododecaphane-19,79-dione (fluorenonophane), exists as a solvate with chlorobenzene, C42H28O6·C6H5Cl. The fluorenonophane contains two fluorenone fragments linked by two m-substituted benzene fragments. Some decrease in its macrocyclic cavity leads to a stacking interaction between the tricyclic fluorenone fragments. In the crystal, the fluorenonophane and chlorobenzene molecules are linked by weak C—H...π(ring) interactions and C—H...Cl hydrogen bonds. The Cl atom of chlorobenzene does not form a halogen bond. A Hirshfeld surface analysis and two-dimensional fingerprint plots were used to analyse the intermolecular contacts found in the crystal structure.

Molecular and Crystal Structures of Some Fluorocymantrenes

The crystal and molecular structures of the fluorocymantrenes [(C5H4F)Mn(CO)3] and [(C5H5−nFn)Mn (CO)2(PPh3)] (n = 1–3) have been studied. The influence of the phosphine for carbonyl substitution on the bond parameters is larger than the influence of the increasing fluorine content. In most cases the Mn → P vector is in a transoid position relative to the fluorine substituents, and therefore the conformational parameters of the PPh3 propeller are in these cases very similar. The crystal structures show many intermolecular C–H⋯O hydrogen bonds and only very few C–H⋯F hydrogen bonds. Graphic Abstract The influence of the phosphine for carbonyl substitution on the bond parameters of the fluorocymantrenes [(C5H4F)Mn(CO)3] and [(C5H5−nFn)Mn (CO)2(PPh3)] (n = 1–3) is larger than the influence of the increasing fluorine content.

Carbonyl pigments: miscellaneous types

Carbonyl pigments are characterized by the presence of one or more carbonyl (C = O) groups in their structures, generally as a component of the chromophoric grouping and as part of an extended conjugated π-electron system. Structurally, they constitute a diverse group of pigments that offer a wide range of colors throughout the spectrum, and most of them provide high levels of technical performance. This paper provides a description of the historical development of thioindigoid, isoindoline, isoindolinone, and quinophthalone pigment types, and discusses their molecular and crystal structures in relation to their properties, the synthetic procedures used in their manufacture and their principal applications. They provide some of the most important high-performance yellow organic pigments for demanding applications in paints, inks, and plastics. Separate individual chapters in this series are devoted the anthraquinonoid, quinacridone, diketopyrrolopyrrole, perylene, and perinone carbonyl pigment subclasses.

Crystal structures of two hydrazide derivatives of mefenamic acid, 3-(2,3-dimethylanilino)-N′-[(E)-(furan-2-yl)methylidene]benzohydrazide and N′-[(E)-benzylidene]-2-(2,3-dimethylanilino)benzohydrazide

The conformation about the central benzene ring in the molecule of (I), C20H19N3O2, is partially determined by an intramolecular N—H...O hydrogen bond. In the crystal, chains parallel to the c axis are generated by intermolecular N—H...O hydrogen bonds with the chains assembled into a three-dimensional network structure by intermolecular C—H...O hydrogen bonds and C—H...π(ring) interactions. The molecule of (II), C22H21N3O, differs from (I) only in the substituent at the hydrazide N atom where a phenylmethylene moiety for (II) is present instead of a furanmethylene moiety for (I). Hence, molecules of (I) and (II) show similarities in their molecular and crystal structures. The conformation of the central portion of the molecule of (II) is also therefore partially determined by an intramolecular N—H...O hydrogen bond and intermolecular N—H...O hydrogen bonds form chains parallel to the c axis. Likewise, the chains are connected into a three-dimensional network by C—H...O hydrogen bonds and C—H...π(ring) interactions.

Mesoionic tetrazolium-5-aminides: Synthesis, molecular and crystal structures, UV–vis spectra, and DFT calculations

Tetrazolium-5-aminides have been prepared by the tert-butylation of 5-aminotetrazole and its N-methyl derivatives by the t-BuOH/HClO4 system followed by the treatment of the tetrazolium salts by alkali. The mesoionic compounds have been found to show a higher reactivity of the exocyclic N atom in comparison with 5-aminotetrazoles. The compounds reacted with 1,2-dibromoethane and 5-(methylsulfonyl)-1-phenyl-1H-tetrazole with substitution of bromine and methylsulfonyl groups giving the corresponding tetrazolium salts or conjugate aminides. The obtained mesoionic tetrazoles have been characterized by elemental analysis, FTIR, NMR, and UV–vis spectroscopy, TGA/DSC analysis and for 1,3-di-tert-butyltetrazolium-5-aminide, its N,N’-ethylene-bridged bis-derivative and (1,3-di-tert-butyl-1H-tetrazol-3-ium-5-yl)(1-phenyl-1H-tetrazol-5-yl)amide by single crystal X-ray analysis. The structural and spectral features of the tetrazolium-5-aminides are discussed by using quantum-chemical calculations.

Can molecular flexibility control crystallization? The case of para substituted benzoic acids

Little is known about the relationship between the kinetic process of nucleation and the molecular and crystal structures of a crystallizing solute. Here we compare the behaviour of a series of benzoic acids with a focus on conformational effects.

Novel tetrazole PtII and PdII complexes with enhanced water solubility: synthesis, structural characterization and evaluation of antiproliferative activity

Novel platinum(II) and palladium(II) chlorido complexes with tetrazole derivatives 1-(2-hydroxyethyl)tetrazole (het) and 1-[tris(hydroxymethyl)methyl]tetrazole (thm), viz. cis-[Pt(het)2Cl2], trans-[Pt(het)2Cl2], trans-[Pt(thm)2Cl2], trans-[Pd(het)2Cl2], and trans-[Pd(thm)2Cl2], were synthesized. The compounds were characterized by elemental and high-resolution electrospray ionization (HRESI) mass spectrometry, high-performance liquid chromatography (HPLC), 1H, 13C and 195Pt nuclear magnetic resonance (NMR) spectroscopy, thermal analyses, and Infrared (IR) spectroscopy. Molecular and crystal structures of trans-[PdL2Cl2] and trans-[PtL2Cl2] (L = het, thm) were established by single-crystal X-ray analysis. The complex cis-[Pt(het)2Cl2] was found to undergo cis–to–trans isomerization upon heating in acetonitrile solution and in the solid state. The synthesized complexes show rather high water solubility lying in the range of 2–10 mg/L.

Cobalt(II) Complexes Based on Benzylmalonate Anions Exhibiting Field-Induced Single-Ion Magnet Slow Relaxation Behavior

The reaction of (NBu4)2Bzmal (where Bzmal2− is benzylmalonate dianion) with Co(OAc)2∙4H2O gives the [Co(Bzmal)(EtOH)(H2O)]n 2D-polymer (1). The addition of 2,2′-bipyridine (bpy) to the starting system results in the [Co(Bzmal)(bpy)2]·H2O·EtOH molecular complex (2). Their molecular and crystal structures were analyzed by single-crystal X-ray crystallography. An analysis of the static magnetic data supported by the SA-CASSCF/NEVPT2 calculations revealed the presence of easy-plane magnetic anisotropy in both complexes. The AC susceptibility data confirm that both complexes show a slow field-induced (HDC = 1000 Oe) magnetic relaxation behavior.