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.

A wide‐range superconductor thermal sensor for low‐temperature measurement

This paper aims at describing a low‐temperature thermal sensor based on superconductor films which can be designed to have required variation of resistance with temperature through an appropriate geometry. Further, it has been shown that the temperature range can be varied to some extent by controlling the bias current.

Technique for measuring the beam shape of pulsed lasers

A simple technique for the measurement of the beam shape parameters of pulsed lasers, with just a single pulse of the laser is described. It involves the use of several beam dividers inclined at very small angles to the beam axis, reflecting the beam back to a screen or a phosphor placed near the exit of the laser. The reflected images are then photographed by a camera to yield the beam parameters.

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

Device for reusing damaged laser mirrors

A simple mirror holder which permits the use of locally damaged laser morrors by allowing the undamaged areas of the reflector to be aligned along the laser optic axis is described. The mirror holder has an eccentric step for housing the mirror and a concentric aperture through which the undamaged surface of the reflector is utilised. By varying the eccentricity and by rotating the mirror inside the step the entire surface area of the reflector can be used successively.

Amplitude Frequency Response Measurement: A Simple Technique

A simple method is described to combine a modern function generator and a digital oscilloscope to configure a setup that can directly measure the amplitude frequency response of a system. This is achieved by synchronously triggering both instruments, with the function generator operated in the ``Linear-Sweep'' frequency mode, while the oscilloscope is operated in the ``Envelope'' acquisition mode. Under these conditions, the acquired envelopes directly correspond to the (input and output signal) spectra, whose ratio yields the amplitude frequency response. The method is easy to configure, automatic, time-efficient, and does not require any external control or interface or programming. This method is ideally suited to impart hands-on experience in sweep frequency response measurements, demonstrate resonance phenomenon in transformer windings, explain the working principle of an impedance analyzer, practically exhibit properties of network functions, and so on. The proposed method is an inexpensive alternative to existing commercial equipment meant for this job and is also an effective teaching aid. Details of its implementation, along with some practical measurements on an actual transformer, are presented.

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.