Bonding in molecular crystals

The electrodynamic forces proposed for stabilizing jellium provide the principal type of bonding in molecular crystals such as solid methane, rare gas crystals, solid anthracene, and the like. These forces also form the inter-chain bonding of long-chain molecules in polymeric materials (the intra-molecular bonding within the chains is usually covalent). 

Kroon J, Ranters JA, Van-Duijneveldt-Van der Rijdt JGCM, Van-Duijneveldt FB, Vliegenthart JA (1975) O-H—O Hydrogen bonds in molecular crystals. Statistical and quantum-chemical analysis. J Molec Struct 24 109-129... 

Desiraju, G.R. (1990) Strength and linearity of C H -O bonds in molecular crystals a database study of some terminal alkynes, / Chem. Soc., Chem. Commun. 454-455. 

Zyss, J., Nicoud, J. R, and Coquillay, M., Chirality and hydrogen bonding in molecular crystals for phase-matched second-harmonic genaration A-(4-Nitrophenyl)-(L)-prolinol (NPP), J. Chem. 

Charge-Assisted Hydrogen Bonds in Molecular Crystals... 

Neutron diffraction determines nuclear coordinates whereas X-ray diffraction refers to maxima of the electron density distribution. A systematic investigation of the differences in bond lengths from X-ray and neutron diffraction analyses of the same crystal structure gave significant differences for dx-dn for C-H and O-H bonds, respectively —0.096(7) and -0.155(10) A (26). This is the reason why the X-ray X-H bond lengths have to be normalized to standard, neutron diffraction, values for the interpretation of hydrogen bonding in molecular crystals. 

Wojcik, A. 1976. Theory of the infrared spectra of the hydrogen bond in molecular crystals. Int. J. Quant. Chem. 10 747-760. 

This type of argument leads us to picture a metal as an array of positive ions located at the crystal lattice sites, immersed in a sea of mobile electrons. The idea of a more or less uniform electron sea emphasizes an important difference between metallic bonding and ordinary covalent bonding. In molecular covalent bonds the electrons are localized in a way that fixes the positions of the atoms quite rigidly. We say that the bonds have directional character— the electrons tend to remain concentrated in certain regions of space. In contrast, the valence electrons in a metal are spread almost uniformly throughout the crystal, so the metallic bond does not exert the directional influence of the ordinary covalent bond. 

Computer simulations therefore have several inter-related objectives. In the long term one would hope that molecular level simulations of structure and bonding in liquid crystal systems would become sufficiently predictive so as to remove the need for costly and time-consuming synthesis of many compounds in order to optimise certain properties. In this way, predictive simulations would become a routine tool in the design of new materials. Predictive, in this sense, refers to calculations without reference to experimental results. Such calculations are said to be from first principles or ab initio. As a step toward this goal, simulations of properties at the molecular level can be used to parametrise interaction potentials for use in the study of phase behaviour and condensed phase properties such as elastic constants, viscosities, molecular diffusion and reorientational motion with maximum specificity to real systems. Another role of ab initio computer simulation lies in its interaction... 

Braga D, Maini L, Polito M, Grepioni F (2004) Hydrogen Bonding Interactions Between Ions A Powerful Tool in Molecular Crystal Engineering 111 1-32 Brechin EK, see Aromf G (2006) 122 1-67... 

In molecular crystals, there are two levels of bonding intra—within the molecules, and inter—between the molecules. The former is usually covalent or ionic, while the latter results from photons being exchanged between molecules (or atoms) rather than electrons, as in the case of covalent bonds. The hardnesses of these crystals is determined by the latter. The first quantum mechanical theory of these forces was developed by London so they are known as London forces (they are also called Van der Waals, dispersion, or dipole-dipole forces). 

Hydrogen Bonding Interactions Between Ions A Powerful Tool in Molecular Crystal Engineering... 

Organic solids have received much attention in the last 10 to 15 years especially because of possible technological applications. Typically important aspects of these solids are superconductivity (of quasi one-dimensional materials), photoconducting properties in relation to commercial photocopying processes and photochemical transformations in the solid state. In organic solids formed by nonpolar molecules, cohesion in the solid state is mainly due to van der Waals forces. Because of the relatively weak nature of the cohesive forces, organic crystals as a class are soft and low melting. Nonpolar aliphatic hydrocarbons tend to crystallize in approximately close-packed structures because of the nondirectional character of van der Waals forces. Methane above 22 K, for example, crystallizes in a cubic close-packed structure where the molecules exhibit considerable rotation. The intermolecular C—C distance is 4.1 A, similar to the van der Waals bonds present in krypton (3.82 A) and xenon (4.0 A). Such close-packed structures are not found in molecular crystals of polar molecules. 

A great number of olefinic compounds are known to photodimerize in the crystalline state (1,2). Formation of a-truxillic and / -truxinic acids from two types of cinnamic acid crystals was interpreted by Bernstein and Quimby in 1943 to be a crystal lattice controlled reaction (5). In 1964 their hypothesis on cinnamic acid crystals was visualized by Schmidt and co-workers, who correlated the crystal structure of several olefin derivatives with photoreactivity and configuration of the products (4). In these olefinic crystals the potentially reactive double bonds are oriented in parallel to each other and are separated by approximately 4 A, favorable for [2+2] cycloaddition with minimal atomic and molecular motion. In general, the environment of olefinic double bonds in these crystals conforms to one of three principal types (a) the -type crystal, in which the double bonds of neighboring molecules make contact at a distance of -3.7 A across a center of symmetry to give a centrosymmetric dimer (1-dimer) (b) the / -type crystal, characterized by a lattice having one axial length of... 

In molecular crystals held together by ionic forces (for instance, salts of organic acids) or polar forces such as hydrogen bonds (for instance, alcohols and amides), the two influences, shape and distribution of forces, may not co-operate, and it is difficult to form any definite conclusions on the structure from crystal shape and cleavage, though it is well to keep these properties in mind during structure determination, for any suggested structure should account for them. 

---