The structures and transition behaviors of the linear long chain primary bromides of even carbon atoms from 1-bromodocosane to 1-bromooctacosane were studied by X-ray powder diffraction method at various temperatures from ordinary temperature to their melting points, and the solid state transition mechanism of the compounds was discussed.
Crystal structures at room temperature of all the bromides studied here belong to monoclinic system. On the assumption that the
c-axis of the unit cell is parallel to the chain axes of the molecules, the lattice constants
a (5.51Å),
b (7.44Å) and β (117°) are found to be the same within the experimental erorr for all the bromides. The values of the lattice constant
c increase with the increasing carbon number of the bromides, 62.4Å for 1-bromodocosane, 67.7Å for 1-bromotetracosane, 72.4Å for 1-bromohexacosane and 78.0Å for 1-bromooctacosane. The
c values indicate an arrangement of double layer of molecules.
Crystal structures of 1-bromodocosane and 1-bromotetracosane at higher temperatures belong to hexagonal system. The basal planes have the same size in both compounds. The lattice constant
c of 1-bromodocosane and 1-bromotetracosane are 63.5Å and 67.8Å, respectively. The structures of 1-bromohexacosane and 1-bromooctacosane belong to monoclinic system. Assuming that the crystal axis
c is parallel to the molecular chain axes, the lattice constants
a,
b,
c and β in these compounds can be determind as follows;
a=4.92Å,
b=8.20Å,
c=72.3Å and β=98° for 1-bromohexacosane,
a=5.12Å,
b=8.22Å,
c=77.6Å and β=104° for 1-bromooctacosane.
The mechanism of the solid state phase transition of 1-bromodocosane and 1-bromotetracosane can be interpreted as follows. At their transition points the lattice constants
a and
b change and the
c axis of the crystal is thought to become perpendicular to the basal plane. This transition phenomenon refer to the rotational transition as a molecular rotation around the chain axis. A similar mechanism of the transition could be applied for 1-bromohexacosane and 1-bromooctacosane.
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