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In-situ cryo-crystallographic techniques have been successfully applied to the determination of the crystal structures of compounds which are liquids at room temperature. It has become possible, using this approach to analyze intermolecular interactions of molecular species without the involvement of solvent either as a promoter for crystal growth or as incorporated solvatomorph [1]. 2-bromo-2chloro-1,1,1-trifluoroethane (Halothane) is a clinically used anesthetic, which has been studied earlier by in situ pressure frozen method using a diamond anvil setup. The crystals were found to belong to triclinic (space group P-1) system [2]. The crystals generated in our experiment belong to a monoclinic system (space group C2/c) with a = 18.6626(1) Å, b = 4.5759(1) Å, c = 12.4030(2) Å, β =91.85°, and V=1058.59(12) Å3, thus generates a new polymorphic form. In this structure the bromine and chlorine atoms are substitutionally disordered similar to that found in the in situ pressure frozen polymorph and the occupancies of bromine and chlorine at each site refine to 52:48 ratio. The packing is through several F....F and Cl/Br....F contacts resulting in tetrameric units as shown below.

Supramolecular chemistry of anti-HIV nucleoside drugs: toward smart crystal phases and self-assembled DNA-mimicries