Simulation of diffuse scattering in DL-norleucine

The diffraction patterns of DL-norleucine (SR-2-aminohexanoic acid, DL-Nle) crystals may show obvious diffuse scattering, usually described as `streaking', between the Bragg peaks. This phenomenon is obviously related to the non-ideal behaviour of the crystal. The normal interpretation is disorder in the stacking of weakly interacting 2D layers, known also for a number of other racemates of amino acids with linear hydrophobic side chains, as well as 1:1 complexes between different L- and D-enantiomers (quasi-racemates). Presented here is the first attempt to extract the information hidden in the diffuse scattering for this group of compounds by applying Monte Carlo simulations to the site distributions of two polymorphs in a block of 48 × 48 × 48 unit cells (four sites in each unit cell, 442 368 in total). The results demonstrate that it is indeed possible to model the diffuse scattering and relate it to processes expected to take place during phase transitions, characterized by slipping of molecular bilayers (or parts of them) relative to their neighbours. The understanding of the (intermediate) mixed phases in terms of domain size and defect density is consequently brought to a new level

Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions

Cooperative effects in two-dimensional cyclic networks containing intermolecular three-centered hydrogen bonding interactions of the type H1&#;A&#;H2 are investigated by means of ab intio molecular orbital and density functional theory calculations. Ring-like clusters consisting of three and up to nine monomers of the cis–cis isomer of carbonic acid H2CO3 are used as basic models, where each unit acts simultaneously as a double hydrogen-bond donor and double hydrogen-bond acceptor. Cooperative effects based on binding energies are evident for (H2CO3)n, where n goes from 2 to 9. Thus, the ZPVE-corrected dissociation energy per bifurcated hydrogen bond increases from 11.52 kcal/mol in the dimer to 20.42 kcal/mol in the nonamer, i.e., a 77% cooperative enhancement. Cooperative effects are also manifested in such indicators as geometries, and vibrational frequencies and intensities. The natural bond orbital analysis method is used to rationalize the results in terms of the substantial charge delocalization taking place in the cyclic clusters. Cooperativity seems close to reaching an asymptotic limit in the largest ring considered, n=9

Tunable Porous Organic Crystals: Structural Scope and Adsorption Properties of Nanoporous Steroidal Ureas

Previous work has shown that certain steroidal bis-(N-phenyl)ureas, derived from cholic acid, form crystals in the P61 space group with unusually wide unidimensional pores. A key feature of the nanoporous steroidal urea (NPSU) structure is that groups at either end of the steroid are directed into the channels and may in principle be altered without disturbing the crystal packing. Herein we report an expanded study of this system, which increases the structural variety of NPSUs and also examines their inclusion properties. Nineteen new NPSU crystal structures are described, to add to the six which were previously reported. The materials show wide variations in channel size, shape, and chemical nature. Minimum pore diameters vary from ∼0 up to 13.1 Å, while some of the interior surfaces are markedly corrugated. Several variants possess functional groups positioned in the channels with potential to interact with guest molecules. Inclusion studies were performed using a relatively accessible tris-(N-phenyl)urea. Solvent removal was possible without crystal degradation, and gas adsorption could be demonstrated. Organic molecules ranging from simple aromatics (e.g., aniline and chlorobenzene) to the much larger squalene (Mw = 411) could be adsorbed from the liquid state, while several dyes were taken up from solutions in ether. Some dyes gave dichroic complexes, implying alignment of the chromophores in the NPSU channels. Notably, these complexes were formed by direct adsorption rather than cocrystallization, emphasizing the unusually robust nature of these organic molecular hosts