Colin R. Pulham

An exploration of the polymorphism of piracetam using high pressure

High-pressure recrystallisation of aqueous and methanolic solutions of piracetam (2-oxo-pyrrolidineacetamide) contained in a diamond-anvil cell at pressures of 0.07–0.4 GPa resulted in the formation of a new high-pressure polymorph of piracetam that has been characterised by in situ X-ray diffraction. The molecular packing arrangement of the new form is very different from those of forms I, II, and III, and the piracetam molecules also adopt a very different conformation in this new phase. Depressurisation to ambient pressure resulted in the formation of form II via a single-crystal to single-crystal transition. By contrast, crystallisation of piracetam from water at ambient pressure resulted in the formation of a new monohydrate of piracetam, which has been characterised by single crystal X-ray diffraction.

High-pressure polymorphism in L-cysteine: the crystal structures of L-cysteine-III and L-cysteine-IV.

The crystal structure of the orthorhombic phase of L-cysteine (hereafter L-cysteine-I) consists of chains of molecules linked via NH...O hydrogen bonds. The chains are linked into a layer by other NH...O hydrogen bonds, forming R4(4)(16) ring motifs. The layers are linked by further NH...O and disordered SH...S/SH...O interactions. The main effects of compression to 1.8 GPa are to contract voids in the middle of the R4(4)(16) rings and to reduce S...S distances from 3.8457 (10) to 3.450 (4) angstroms. The latter is at the lower limit for S...S distances and we suggest that strain about the S atom is responsible for the formation of a new phase of L-cysteine, L-cysteine-III, above 1.8 GPa. The phase transition is accompanied by a change in the NCCS torsion angle from ca 60 to ca -60 degrees and small positional displacements, but with no major changes in the orientations of the molecules. The structure of L-cysteine-III contains similar R-type ring motifs to L-cysteine-I, but there are no S...S contacts within 3.6 angstroms. L-Cysteine-III was found to be stable to at least 4.2 GPa. On decompression to 1.7 GPa, another single-crystal to single-crystal phase transition formed another previously uncharacterized phase, L-cysteine-IV. This phase is not observed on increasing pressure. The structure consists of two crystallographically independent cysteine molecules in the same conformations as those found in L-cysteine-I and L-cysteine-III. The structure separates into zones with are alternately phase I-like and phase III-like. L-Cysteine-IV can therefore be thought of as an unusual example of an intermediate phase. Further decompression to ambient pressure generates L-cysteine-I.

High-pressure recrystallisation—a route to new polymorphs and solvates

The recrystallisation of organic compounds from solution under high-pressure conditions is shown to be a versatile method for the formation of new polymorphs and solvates. The technique is illustrated by the crystallisation of a new polymorph of phenanthrene from dichloromethane at a pressure of 0.7 GPa, and the crystallisation of a novel dihydrate of paracetamol from water at a pressure of 1.1 GPa. These phases have been characterised by single crystal X-ray diffraction. We also demonstrate that the technique can be used to prepare a polymorph that is metastable under ambient conditions. Thus the orthorhombic form of paracetamol was crystallised from ethanol at a pressure of 1.1 GPa.

Temperature- and Pressure-induced Proton Transfer in the 1:1 Adduct Formed between Squaric Acid and 4,4 '-Bipyridine

We have applied a combination of spectroscopic and diffraction methods to study the adduct formed between squaric acid and bypridine, which has been postulated to exhibit proton transfer associated with a single-crystal to single-crystal phase transition at ca. 450 K. A combination of X-ray single-crystal and very-high flux powder neutron diffraction data confirmed that a proton does transfer from the acid to the base in the high-temperature form. Powder X-ray diffraction measurements demonstrated that the transition was reversible but that a significant kinetic energy barrier must be overcome to revert to the original structure. Computational modeling is consistent with these results. Modeling also revealed that, while the proton transfer event would be strongly discouraged in the gas phase, it occurs in the solid state due to the increase in charge state of the molecular ions and their arrangement inside the lattice. The color change is attributed to a narrowing of the squaric acid to bipyridine charge-transfer energy gap. Finally, evidence for the possible existence of two further phases at high pressure is also presented.

The hydrides of aluminium, gallium, indium, and thallium: a re-evaluation

boron gives little hint of the comparative wasteland making up much of the hydride estate of the heavier Group 13 elements., At a recent count2 about 100 binary boranes are now known, typically as discrete molecules remarkable for their stoicheiometries and structures which have done much to challenge and reshape our understanding of chemical bonding at large. By contrast, aluminium forms only one binary hydride stable under normal conditions as a polymeric solid, [AIH,],, the a-form of which is isostructural with AlF,, featuring 6-coordinate aluminium atom^.^^^ Attempts to prepare the analogous gallium compound have a chequered hist~ry,~ and it has taken nearly 50 years from the first reported sighting to establish the true credentials of gallane, [GaH,],,6 which now emerges as showing obvious affinities to diborane in the vapour state (i.e. n = 2) while being relatively short-lived under normal conditions. Despite some claims, however, it is unlikely that the hydrides [JnH,], and [TlH,], have yet materialized. In this account we review the current status of the hydrides formed by the Group 13 metals aluminium, gallium, indium, and thallium. Coordinatively saturated derivatives like MH, (M = Al, Ga, In, or T1) and Me,N. MH, (M = A1 or Ga) having been known for some year^,^?^ we are concerned primarily with the parent hydrides, [MH,], (m = 1, 2, or 3; n = 1, 2...), and related unsaturated derivatives. The last category includes species with more than one Group 13 element, for example tetrahydroborate derivatives like Al(BH,), and H,Ga(BH,),-, (m = 1 or 2) and tetraborane(l0) derivatives like 2-R2MB,H, (M = Al, R = Me; M = Ga, R = H or Me). It is appropriate first to consider the physical properties of the binary hydrides [MH,],. Hence it is possible to identify not only feasible methods of synthesizing compounds with M-H bonds, but also the origins of the thermal lability and reactivity besetting such compounds. 1.1 Theoretical Modelling Exploration of the Group 13 metal hydrides has been spurred by the greatly enhanced sophistication of modern computational methods which now admit the use of relatively elaborate basis sets, as well as making due allowance for factors like configuration interaction and relativistic correction^.^ Where comparisons can be made, such calculations typically yield dimensions and energetics which reproduce closely the experimental findings, and in some cases improve upon those findings. Such is the case, for example, with the monohydride molecules MH (M = B, Al, Ga, In, or Tl), which are short-lived under normal condition^.^,^ Accordingly we can place some trust in such results to anticipate the likely equilibrium molecular structures, vibrational properties, and binding energies of Group 13 hydrides, including numerous species whose existence has yet to be authenticated. Just what inferences are to be drawn will be discussed in Section 2.

Putting pressure on elusive polymorphs and solvates

The reproducible crystallisation of elusive polymorphs and solvates of molecular compounds at high pressure has been demonstrated through studies on maleic acid, malonamide, and paracetamol. These high-pressure methods can be scaled-up to produce ‘bulk’ quantities of metastable forms that can be recovered to ambient pressure for subsequent seeding experiments. This has been demonstrated for paracetamol form II and paracetamol monohydrate. The studies also show that the particular solid form can be tuned by both pressure and concentration.

Pressure-cooking of explosives-the crystal structure of epsilon-RDX as determined by X-ray and neutron diffraction

The high-pressure, high-temperature epsilon-form of the widely used explosive RDX has been structurally characterised using a combination of diffraction techniques, and a sample of this form has been successfully recovered to ambient pressure.

The Hunting of the Gallium Hydrides

Publisher Summary This chapter provides an overview of gallane and its derivatives. Monochlorogallane has indeed been the turning point in the hunt for gallane and its derivatives. It reacts in vacuo with lithium tetrahydrogallate at 243–250 K to give not only substantial quantities of elemental gallium and hydrogen but also gallane in yields up to 50%. The identity of the volatile, thermally perishable product has been established unequivocally by chemical analysis, by its vibrational and 1 H NMR spectra, and by chemical trapping with trimethylamine to give the known molecular adduct (Me 3 N) 2 GaH 3 as the sole product at 178 K. Efforts to improve the yield of gallane by using a solvent to give better control over the metathesis reaction have so far met with only limited success. The choice of medium is restricted by the need to minimize both the basic properties and the susceptibility to reduction of the would-be solvent. Thus, the mildly basic properties characterizing ether may enhance its ability to dissolve the reagents, but only at the expense of producing a sample of the gallane that can be freed from the solvent with difficulty.

Molecular aluminium trihydride, AlH3: generation in a solid noble gas matrix and characterisation by its infrared spectrum and Ab initio calculations

Broad-band photolysis of a solid noble gas matrix containing Al atoms and H2 gives rise to the planar, monomericAlH3 molecule, isotopically natural and deuteriated forms of which have been characterised by their IR spectra; confirmation is afforded by the results of MP2 ab initio and normal coordinate analysis calculations.

High-pressure structural studies of energetic materials

This article reviews how the advances in the techniques for the collection and analysis of high-pressure X-ray and neutron diffraction data, augmented by spectroscopic data, now permit the accurate determination of the full crystal structure of energetic materials under extreme conditions. Using these methods, the crystal structure of the high-pressure γ-form of RDX (1,3,5-trinitrohexahydro-s-triazine) has been determined–the first case of a high-pressure structure of an energetic material. In addition, the crystal structure of the highly metastable β-form has been determined and, contrary to the previous reports, has been shown to be different from the form obtained at elevated temperatures and pressures.