The disorder of perfluoroalkyl chains in crystals: Two case histories of interpretation and refinement

Perfluoroalkyl chains in solids are highly disordered in a wide range of temperatures. Poor attention is typically given to this problem in crystallographic studies to the point that no attempt is frequently made in order to model the collected data and disorder remains even unmentioned in a large number of single crystal reports. This paper presents a short analysis of the problems related with this disorder. Two simple crystal structures, namely the halogen bonded adducts between N,N,N′,N′-tetramethyl-1,4-phenylendiamine and α,ω-diiodoperfluorobutane or α,ω-diiodoperfluorohexane are discussed in details in order to suggest some simple and basic principles for the refinement of perfluoroalkyl chains in single crystal structural studies.     

Halide anions driven self-assembly of haloperfluoroarenes: Formation of one-dimensional non-covalent copolymers

The supramolecular organization in six solid assemblies involving iodo- and bromoperfluoroarene derivatives is described. Single crystal X-ray analyses show that the formation of the supramolecular architectures is controlled by I⁻?Br–Ar_F, I⁻?I–Ar_F, Br⁻?I–Ar_F, and Cl⁻?I–Ar_F halogen bondings thus proving the X⁻?X′–Ar_F supramolecular synthon, where X can be the same as or different from X′, is particularly robust. In five of the described architectures halide anions form two halogen bondings and form infinite chains wherein dihaloperfluoroarenes, which function as bidentate electron acceptors, and halide anions, which function as bidentate electron donors, alternate. This behaviour shows halide anions have a fair tendency to work as bidentate halogen bonding acceptors.     

Hybrid iodoperfluoroalkane-ferrocene supramolecular arrays: the shortest contacts iodine forms with nitrogen atoms and unsaturated moieties

α,ω-Diiodoperfluoralkanes self-assemble in solution and in the solid phase with (S)-(−)-N,N-dimethyl-1-ferrocenylethylamine. The formed adducts have been characterized by DSC, IR, Raman, and NMR techniques. Single crystal X-ray analysis of one of the obtained adducts shows that perfluorinated and organometallic modules alternate giving rise to infinite one-dimensional (1D) chains. The interacting modules are connected through strong n-type halogen bondings, involving nitrogen and iodine atoms, and weak π-type halogen bondings, involving Cp rings and iodine atoms. Both interactions are the shortest reported to now in their respective classes. Theoretical calculations have been performed to quantify the observed π-type halogen bonding. For the first time a metallocene-perfluorocarbon (PFC) hybrid material is described.     

Comparison by mass spectrometry of ring cleavage in barbituric acid and 5-fluorobarbituric acid derivatives

The mass spectrometric behaviour of barbituric acid and 1,3-dimethylbarbituric acid was compared with that of the corresponding 5,5-difluoro derivatives and of some 5-fluoro-5-alkyl derivatives in order to study the influence of fluorine in the fragmentation processes. This investigation, performed using both electron impact ionization and positive- and negative-ion fast atom bombardment, evidences well the role of fluorine in barbiturate ring bond cleavages.     

Synthesis of optically pure α-halo-α′-sulphinyl-ketones

When optically pure sulphinyl carbanions are reacted at ?75°C with α-chloro or α-bromo carboxylic acid esters addition on the carboxyl group occurs and corresponding α-halo-α′-sulphinyl-ketones are obtained in optically pure form.     

Perfluorocarbon-Hydrocarbon Discrete Intermolecular Aggregates: An Exceptionally Short N⋯I Contact

1-Iodoperfluoroheptane ( 1a ) and tetramethylethylenediamine ( 2 , TMEDA) form the 2:1 ratio stable aggregate 3a and a similar behaviour is shown by 1-iodoperfluoroalkanes 1b-e and iodopentafluorobenzene 1f . These aggregates have been characterised in solution by 1 H/ 19 F-NMR spectroscopy and in the solid state through IR and single crystal X-ray diffraction. The determined structure of 3a (triclinic, a =6.2283(10), b =9.250(2), c =15.098(3) Å, f =81.369(5), g =81.397(5), n = 86.010(5), V =849.3(3) A m 3 , T =175(3) K, space group P-1 (No. 2), Z =1; d (calc)=2.167 g cm m 3 ; 4121 independent reflections, 3665 with I o >2( I o ); final refinement gave R1=0.0400, wR2=0.0901) showed the second shortest N > I interaction found in the crystallographic literature [2.762(3) Å] and the interdigitation of perfluorocarbon and hydrocarbon modules due to co-operative -C-H > F-C- interactions. Calculations to quantify these latter interactions have been also performed.     

Engineering functional materials by halogen bonding

Engineering functional materials endowed with unprecedented properties require the exploitation of new intermolecular interactions, which can determine the characteristics of the bulk materials. The great potential of Halogen Bonding (XB), namely any noncovalent interaction involving halogens as electron acceptors, in the design of new and high‐value functional materials is now emerging clearly. This Highlight will give a detailed overview on the energetic and geometric features of XB, showing how some of them are quite constant in most of the formed supramolecular complexes (e.g., the angle formed by the covalent and the noncovalent bonds around the halogen atom), while some others depend strictly on the nature of the interacting partners. Then, several specific examples of halogen‐bonded supramolecular architectures, whose structural aspects as well as applications in fields as diverse as enantiomers' separation, crystal engineering, liquid crystals, natural, and synthetic receptors, will be fully described. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: PolymChem 45: 1–15, 2007     

Synthesis of optically pure α-methylene-γ-lactones from (+)-R-(4-methylphenyl)-alkylsulphoxides

Optically pure (+)-R-(4-methylphenyl)sulphoxides were lithiated and alkylated with lithium α-bromomethyl acrylate with medium to high diastereoselection; condensation products gave in two steps optically pure α-methylene-γ-lactones.