R. Céolin

A new hexagonal phase of fullerene C60

Abstract A new phase of fullerene C 60 with a simple hexagonal unit cell with 6/mmm symmetry was grown by slowly evaporating solutions of C 60 in dichloromethane. X-ray measurements reveal that the c / a ratio is 1.616 at 298 K and increases as temperature decreases. At low temperature, it seems to extrapolate to 1.633, the ideal ratio for a close-packed hexagonal lattice. The unit cell volume which is higher than that of the usual cubic C 60 phases at high temperature decreases near 90 K. A structural model is proposed according to which a 3-fold molecular axis is parallel to the 6-fold crystallographic z -axis. This suggests that the molecules could reorient around this axis at high temperature.

Decagonal C60 crystals grown from n-hexane solutions: solid-state and aging studies

Abstract Decagonal C60 crystals grown from n-hexane solutions correspond to an orthorhombic 1:1 solvate (a=10.249 A, b=31.308 A, c=10.164 A). It forms with negative excess volume ( −55.5 A 3 per formula unit) and transforms on heating into fcc C60 (desolvation enthalpy of +50.6 kJ per solvate mole, close to the sublimation enthalpy for pure n-hexane) while n-hexane desorption from fcc C60 is accompanied by an enthalpy of +48.6 kJ per solvent mole. Thus solvate formation is preferred to solvent adsorption. Orthorhombic C 60 ·1 n -hexane undergoes no degradation when stored in air for 9 years at room temperature in the dark.

Solid-state studies on C60 solvates grown from n-heptane

Crystallographic and thermodynamic experiments show that crystalline C60 obtained by slow evaporation of solutions in n-heptane is a C60, n-heptane 1:1 solvate. Its lattice is hexagonal, Laue class 6/mmm, with a = 10.00(4) A and c = 10.16(1) A. No transition is observed at temperatures higher than 100 K, and desolvation into fcc C60 occurs at about 360 K with ΔH = +43.5 J g−1, close to the sublimation enthalpy for pure n-heptane. Another binary compound, presumably a polymorph of the former, is sometimes obtained by rapid evaporation of toluene + n-heptane mixtures. Its lattice is orthorhombic, Immm, with a = 10.07 A, b = 10.22 A and c = 48.9 A.

An order–disorder phase transition in the van der Waals based solvate of C60 and CClBrH2

The co-crystal of C60·2CBrClH2 possesses a monoclinic (C2/m) structure at room temperature with both molecular entities, C60 and CBrClH2, orientationally ordered. At 322 K, it transforms reversibly into a hexagonal (P6/mmm) setting, revealing a rare example of a heteromolecular stator–rotator transition in a fullerene co-crystal, which applies to both the fullerene and the coformer analogous to the paradigmatic C60–cubane co-crystal. However, in the present case, topological molecular surface matching between the two chemical species is not necessary and the order–disorder phase transition reflects simultaneous activation of the orientational disorder of both C60 and CBrClH2.

Pressure-temperature phase diagram of the dimorphism of the anti-inflammatory drug nimesulide

Understanding the phase behavior of active pharmaceutical ingredients is important for formulations of dosage forms and regulatory reasons. Nimesulide is an anti-inflammatory drug that is known to exhibit dimorphism; however up to now its stability behavior was not clear, as few thermodynamic data were available. Therefore, calorimetric melting data have been obtained, which were found to be TI-L=422.4±1.0K, ΔI→LH=117.5±5.2Jg-1,TII-L=419.8±1.0K and ΔII→LH=108.6±3.3Jg-1. In addition, vapor-pressure data, high-pressure melting data, and specific volumes have been obtained. It is demonstrated that form II is intrinsically monotropic in relation to form I and the latter would thus be the best polymorph to use for drug formulations. This result has been obtained by experimental means, involving high-pressure measurements. Furthermore, it has been shown that with very limited experimental and statistical data, the same conclusion can be obtained, demonstrating that in first instance topological pressure-temperature phase diagrams can be obtained without necessarily measuring any high-pressure data. It provides a quick method to verify the phase behavior of the known phases of an active pharmaceutical ingredient under different pressure and temperature conditions.