Transitions de phase destructive et non destructive dans le cristal moleculaire bromo-2 naphtalene

The polymorphism of 2-bromonaphthalene has been studied by both crystallographic and energetical methods. Three crystalline forms have been characterized, respectively denoted Br_III, Br_II and Br_I. The first one is the stable form up to 319 K. At this temperature a first order phase transition occurs which breaks the single crystal and leads to a disordered structure Br_I isotypic with the naphthalene one. The Br_II form is a metastable one which appears when cooling the Br_I, form; when so formed, the Br_II phase can give again the Br_I one by annealing; so that the Br_I-Br_II transition is reversible. This second order transition extends over a large temperature range (275–319 K), it does not destroy the single crystal and corresponds to a substructural modification along the c axis of the monoclinic cell. The anomalies of the Cp curve and the variations of the principal components of the thermal expansion tensor suggest that there are two competitive temperature dependent molecular reorientations. The transition Br_II→Br_III which leads to the stable ordered form is spontaneous at room temperature, it takes place sluggishly and destroys the single crystal.Cell parameters of the Br_III form have been determined from powder data using an automatic indexing method: a = 9.578(1) Å, B = 9.601(1) Å, c = 10.303(1) Å, α = 100.79(1)°, β = 109.06(1)°, γ = 101.77(1)°. (Figure of merit M₂₀ = 86.)