1. Structure-melting relations in isomeric dibromobenzenes.
- Author
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Dziubek, Kamil F. and Katrusiak, Andrzej
- Subjects
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MELTING , *HIGH temperatures , *HALOGENS , *CHEMICAL bonds , *X-ray diffraction , *SPACE groups , *ISOMERS - Abstract
1,4-Dibromobenzene melts at a considerably higher temperature than the 1,2- and 1,3-isomers. This melting-point difference is consistent with the molecular symmetry, as described by Carnelley's rule, and with the frequency of Br...Br halogen bonds. The lowest melting point of 1,3-dibromobenzene correlates with its two symmetry-independent molecules, indicating their inability to pack closely. Single crystals of 1,2- and 1,3-dibromobenzene have been grown under isochoric conditions in a diamond-anvil cell and at isobaric conditions in a glass capillary. Their structures have been determined in situ by X-ray diffraction. At 295 K 1,2-dibromobenzene crystallizes at 0.2 GPa as orthorhombic, space group Pbca, Z′ = 1, and 1,3-dibromobenzene at 0.3 GPa as orthorhombic, space group P212121, Z′ = 2. The same crystal phases are formed at ambient pressure by freezing these liquids below 256.15 and 248.45 K, respectively. The third isomer, 1,4-dibromobenzene, is a solid at room temperature and crystallizes as monoclinic, space group P21/ a. Striking relations between the structures and melting points of the corresponding dibromobenzene and dichlorobenzene isomers have been discussed. [ABSTRACT FROM AUTHOR]
- Published
- 2014
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