Using Water as a Design Element in Crystal Engineering. Host-Guest Compounds of Hydrated 3,5-Dihydroxybenzoic Acid

Thirteen host guest compounds of 3,5-dihydroxybenzoic acid (DHBA) have been structurally characterized. Water molecules occupy the peripheries of a hexagonal void, created with DHBA molecules, and act as ``hooks'' to connect the guest molecules with the host-framework via hydrogen bonding. The ``water hook'' is an OH group acting as a donor. Consequently, the guest molecules were chosen so that they contain good hydrogen bond acceptor functionalities. A number of multicomponent hydrates were isolated with stoichiometries (DHBA)(x)(H2O). (guest),. Of these, compounds with the following as guests were obtained as crystals that were good enough for single crystal work: ethyl acetate (EtOAc), diethyl oxalate, dimethyl oxalate, di(n-propyl) oxalate, diethyl malonate, diethyl succinate, chloroacetonitrile, N,N-dimethyl formamide (DMF), acetone, dimethyl sulfoxide (DMSO), 1-propanol, and 2-butanol. From 2-butanol, a hemihydrate, (DHBA)(2)(H2O), was also obtained concomitantly. Further to guest stabilization, water acts as a good mediator of effective crystal packing and also determines the topology of the host framework. En the present series of compounds, the role of water is wide ranging, and it is not easy to classify it specifically as a host or as a guest.

Crystal engineering: A brief overview

Crystal structures of organic and metal-organic compounds have been determined in enormous numbers over the past century, and at the time of writing this review, the Cambridge Structural Database has just crossed the half million mark. The possibility of designing a particular crystal packing is, however, of more recent origin and the subject of crystal engineering has addressed this possibility, more or less systematically, during the past 30 years. Crystal engineering demands a detailed and thorough knowledge of intermolecular interactions, which act as the supramolecular glue that binds molecules into crystals. It also requires systematic strategies for the design of a crystal, the architectural blueprint as it were. Finally, this enterprise needs to be geared towards a useful property in that the crystal that is being designed is a functional one. All these features of the subject are directly or indirectly connected with the fact that there is a very large database of known crystal structures that is available to the crystal engineer. This review attempts to briefly survey the current scenario in this expanding subject.

Studies in crystal engineering. Photochemical and crystallographic investigations of bromocoumarins and (±)-7-(p-bromobenzylidene)piperitone

Studies in crystal engineering. Photochemical and crystallographic investigations of bromocoumarins and (±)-7-(p-bromobenzylidene)piperitone

Engineering behavior of uplifted Smectite-rich Cochin and Mangalore marine clays

The present study aims to assess whether the smectite-rich Cochin and Mangalore clays, which were deposited in a marine medium and subsequently uplifted, exhibit consistency limits response typical of expanding lattice or nonexpanding (fixed) lattice-type clays on artificially changing the chemical environment. The chemical and engineering behaviors of Cochin and Mangalore marine clays are also compared with those of the smectite-rich Ariake Bay marine clay from Japan. Although Cochin, Mangalore, and Ariake clays contain comparable amounts of smectite (32-45%), Ariake clay exhibits lower consistency limits and much higher ranges of liquidity indices than the Indian marine clays. The lower consistency limits of the Ariake clay are attributed to the absence of well-developed, long-range, interparticle forces associated with the clay. Also, Ariake clay exhibits a significantly large (48-714 times) decrease in undrained strength on remolding in comparison to Cochin and Mangalore clays (sensitivity ranges between 1 and 4). A preponderance of long-range, interparticle forces reflected in the high consistency limits of Cochin and Mangalore clays (wL range from 75 to 180%) combined with low natural water contents yield low liquidity indices (typically <1) and high, remolded, undrained strengths and are considered to be responsible for the low sensitivity of the Indian marine clays.

Transferability of Multipole Charge Density Parameters for Supramolecular Synthons: A New Tool for Quantitative Crystal Engineering

The modularity of the supramolecular synthon is used to obtain transferability of charge density derived multipolar parameters for structural fragments, thus creating an opportunity to derive charge density maps for new compounds. On the basis of high resolution X-ray diffraction data obtained at 100 K for three compounds methoxybenzoic acid, acetanilide, and 4-methyl-benzoic acid, multipole parameters for O-H center dot center dot center dot O carboxylic acid dimer and N-H center dot center dot center dot O amide infinite chain synthon fragments have been derived. The robustness associated with these supramolecular synthons has been used to model charge density derived multipolar parameters for 4-(acetylamino)benzoic acid and 4-methylacetanilide. The study provides pointers to the design and fabrication of a synthon library of high resolution X-ray diffraction data sets. It has been demonstrated that the derived charge density features can be exploited in both intra- and intermolecular space for any organic compound based on transferability of multipole parameters. The supramolecular synthon based fragments approach (SBFA) has been compared with experimental charge density data to check the reliability of use of this methodology for transferring charge density derived multipole parameters.

Role of organic fluorine in crystal engineering

The design of compounds with novel and improved physico-chemical properties as advanced functional materials with a specific application spectrum requires the knowledge about possible supramolecular packing motifs and their experimental control in crystalline lattice. Besides the structure of the individual molecule, non-covalent interactions play a significant role in the determination of molecular conformation, along with the formation of three-dimensional supramolecular architecture in a crystal as a requirement for molecular recognition processes, and the related bioactivity. Involvement of functional groups will contribute to the formation of a predefined packing motif due to their well-defined interactions. The strength and directionality of these interactions create characteristic packing motifs, which can be used for the design of supramolecular arrangements by the development of appropriate strategies for the precise control of their topology. Most relevant of these non-covalent interactions are stacking interactions and hydrogen bonds, which have been subjects of extensive study in the last two decades. In recent literature, substantial efforts have been put in by various researchers towards the understanding of interactions involving organic fluorine and the role they play in generating different packing motifs which guides assembling of molecules in the crystal lattice.

Sonochemical reaction engineering

Ultrasound has been widely used by chemists to enhance yields as well as rates of homogeneous as well as heterogeneous chemical reactions. The effect of ultrasound on the course of chemical reactions is mediated through cavitation bubbles it generates. High temperatures and pressures are attained inside the cavitating bubbles when they collapse. The extreme conditions so generated lead to the formation of reactive intermediates, e.g., free radiacls, inside the bubbles, which cause chemical reactions to occur when they enter the surrounding liquid. This is the mechanism through which ultrasound influences the path of homogeneous reactions. The cavitation bubbles collapse asymmetrically in the vicinity of solids, e.g., catalyst particles. Asymmetric collapse lead to formation of high speed microjets. The microjets can enhance transport rates, the increase surface area through pitting as well as particle fragmentation through collisions. Both can alter the rates of heterogeneous reaction rates. It however appears that these effects do not exhaust the scope of the influence of ultrasound on heterogeneous reactions. Modelling and quantitative prediction of the effect of ultrasound on chemical reactions is however at a stage of infancy as the phenomena are complex. Only a few examples of modelling exist in literature. Apart from this, reactor design and scaleup pose significant problems. Thus sonochemical reaction engineering offers large scope for research and development efforts.

Studies in crystal engineering: structure�reactivity correlations of substituted styrylcoumarins and related systems

The solid state photochemical behaviour of 7-hydroxy-4-styrylcoumarin 1 and several of its derivatives and analogues has been investigated. All the compounds with the exception of 7-methoxy-4-styrylcoumarin 2 are photolabile and yield anti-HT dimers. It has been observed that chloro substitution in the systems studied does not lead to the expected beta-packing mode. The photobehaviour of 1 and 2 has been correlated with their crystal structures. Reasons for alpha-packing have been examined. The systematics in the arrangement of the carbonyl group and phenyl group of the close neighbours in the crystals of 1, 2 and a few other cases are presented.

Reflections on the Hydrogen Bond in Crystal Engineering

Comments on aspects of the new definition of the hydrogen bond specific to crystal engineering are given.

Crystal Structure Engineering by Fine-Tuning the Surface Energy: The Case of CdE (E = S/Se) Nanocrystals

We prove that CdS nanocrystals can be thermodynamically stabilized in both wurtzite and zinc-blende crystallographic phases at will, just by the proper choice of the capping ligand. As a striking demonstration of this, the largest CdS nanocrystals (similar to 15 nm diameter) ever formed with the zinc-blende structure have been synthesized at a high reaction temperature of 310 degrees C, in contrast to previous reports suggesting the formation of zinc-blende CdS only in the small size limit (< 4.5 nm) or at a lower reaction temperature (<= 240 degrees C). Theoretical analysis establishes that the binding energy of trioctylphosphine molecules on the (001) surface of zinc-blende CdS is significantly larger than that for any of the wurtzite planes. Consequently, trioctylphosphine as a capping agent stabilizes the zinc-blende phase via influencing the surface energy that plays an important role in the overall energetics of a nanocrystal. Besides achieving giant zinc-blende CdS nanocrystals, this new understanding allows us to prepare CdSe and CdSe/CdS core/shell nanocrystals in the zinc-blende structure.

Critical earthquake input power spectral density function models for engineering structures

The problem of determining optimal power spectral density models for earthquake excitation which satisfy constraints on total average power, zero crossing rate and which produce the highest response variance in a given linear system is considered. The solution to this problem is obtained using linear programming methods. The resulting solutions are shown to display a highly deterministic structure and, therefore, fail to capture the stochastic nature of the input. A modification to the definition of critical excitation is proposed which takes into account the entropy rate as a measure of uncertainty in the earthquake loads. The resulting problem is solved using calculus of variations and also within linear programming framework. Illustrative examples on specifying seismic inputs for a nuclear power plant and a tall earth dam are considered and the resulting solutions are shown to be realistic.

Studies in crystal engineering: Effect of fluorine substitution in crystal packing and topological photodimerization of styryl coumarins in the solid state

Styryl coumarins generally yield centrosymmetric (alpha-mode, anti-HT) photodimers when subjected to irradiation in the solid state, However, the substitution of fluorine dramatically alters the packing mode and steers the molecules 4-(4-fluorostyryl)coumarin 1 and 4-(2-fluorostyryl)coumarin 2 to form a stereospecific photodimer, beta-mode, syn-HH across the styrenic double bond (yield 78-85%). The stereochemistry of the photodimer 2a has been established by X-ray crystallography. There is no evidence for the presence of C-H ... F interactions. The true nature of the weak atom-atom interactions called into play when fluorine is substituted is not clear, It is observed that the fluoro substituted compounds have greater crystal density than the corresponding unsubstituted ones.

Some Basic Aspects of Reaction Engineering of Precipitation Processes

Analysis of precipitation reactions is extremely important in the technology of production of fine particles from the liquid phase. The control of composition and particle size in precipitation processes requires careful analysis of the several reactions that comprise the precipitation system. Since precipitation systems involve several, rapid ionic dissociation reactions among other slower ones, the faster reactions may be assumed to be nearly at equilibrium. However, the elimination of species, and the consequent reduction of the system of equations, is an aspect of analysis fraught with the possibility of subtle errors related to the violation of conservation principles. This paper shows how such errors may be avoided systematically by relying on the methods of linear algebra. Applications are demonstrated by analyzing the reactions leading to the precipitation of calcium carbonate in a stirred tank reactor as well as in a single emulsion drop. Sample calculations show that supersaturation dynamics can assume forms that can lead to subsequent dissolution of particles that have once been precipitated.

Growth and development of Thiobacillus ferrooxidans for engineering applications

A bioprocessing approach for the extraction of base, nuclear and precious metals from refractory and lean grade ores has been reviewed in this paper. Characteristic morphological features of Thiobacillus ferrooxidans, the organism which has been extensively used for biooxidation of sulphide ores have been discussed. Mechanisms of chemoautotrophy and mineral oxidation have been illustrated. The current engineering applications of this microorganism have also been brought out. Various methods for accelerating the growth of Thiobacillus ferrooxidans for faster biooxidation and genetic manipulation for development of desired strains have been outlined.