A Packing Model for Interpenetrated Diamondoid Structures—an Interpretation Based on the Constructive Interference of Supramolecular Networks

Abstract

Abstract:The ability to predict and subsequently control solid-state structure has been identified as a major challenge in the field of crystal engineering. Here we suggest the concept of constitutive models as a tool for understanding crystal packings and for designing new solid-state structures. Such models are intended to relate molecular interactions and their geometrical constraints with solid-state organization. These models will most likely be of greatest use for crystals consisting of supramolecular networks, that is, infinite assemblies of small molecules associating adducts of 4,4'-biphenyldicarbonitrile through strong, directional, and selective with silver(1) salts. Observed structural denoncovalent interactions. The concept of formations induced by counterions of the constitutive packing model is illustrat-varying size may be understood in terms ed for interpenetrated diamondoid coor-of the interference of two supramolecular dination networks based on crystalline networks within this system: the diamondoid metal-ligand coordination network and face-to-face aromatic stacks of the organic ligand. The constitutive model developed here has been applied to other diamondoid coordination networks in the literature and is found to be general.

Crystal Packing in Di‐(μ‐OH)‐ortho‐palladated Complexes – A DFT Insight into the Molecular Structure and Solid‐State Interactions

“…A last important conclusion that can be drawn from the study of model systems 3 is that, at the working level of theory, we have not been able to find any minimum corresponding to a hypothetical tetrameric derivative 3 4 upon interaction of either two units of dimer 3 2 or one trimer 3 3 with a monomer 3 1 . This would explain the preferential formation of trimeric units as energetically most favored species in the solid-state crystalline structure of 1.…”

“…The relative spatial orientation of the hydroxy group closest to the N atoms seems to be less energy-determining: there is only a small destabilization when it is oriented cis relative to the other one, especially in the proximity of the absolute minimum. Moving one step further, all model monomers 3 1 have at their outer (convex) surface two hydroxy groups oriented in such a way that could act simultaneously as hydrogen donor and/or acceptor towards a suitable complementary second monomeric unit 3 1 giving rise to a dimeric molecule 3 2 . In the example shown in Figure 7, the recognition process between two units of self-complementary 3 1 trans leading to dimer 3 2 t-th is represented in the following way: both precursor molecules are displayed as electrostatic potential (from -0.1, white, to +0.1 a.u., black) mapped onto their respective electron density isosurfaces (0.0075 isovalue).…”

“…[1][2][3][4][5][6] The order of stability in the interaction of two π systems has been found to be π-deficient-π-deficient Ͼ π-deficient-π-rich Ͼ π-rich-π-rich. [7] In the systems under study, a nitrogen heteroatom within a six-membered ring introduces an electron-withdrawing perturbation.…”

From 2D hyperbolic forests to 3D Euclidean entangled thickets

“…These entangled thickets also offer novel models for crystals containing multiple frameworks, found, for example, in molecular crystals [38]. Indeed, the thicket consisting of four interwoven identical enantiomers of Y * on the D surface (Sect.…”

Crystal engineering of lattice metrics of perhalometallate salts and MOFs

“…There has been limited success in this endeavor, but the work in this field of Ward (1-3) and Metrangolo and Resnati (4,5) is notable, and builds on that of Yaghi (6), Zaworotko, (7) Moore (8), Fujita (9) and Jones (10) in seeking control over lattice metrics in crystal structures. In all these cases the lattice metrics are determined by the replacement of a particular molecular unit by another of different dimensions, leading to a discrete change in the lattice dimensions.…”