Relative influence of noncovalent interactions on the melting points of a homologous series of 1,2-dibromo-4,5-dialkoxybenzenes.

Crystal structures are presented for two members of the homologous series of 1,2-dibromo-4,5-dialkoxybenzenes, viz. those with decyloxy and hexadecyloxy substituents, namely 1,2-dibromo-4,5-bis(decyloxy)benzene, C(26)H(44)Br(2)O(2), (II), and 1,2-dibromo-4,5-bis(hexadecyloxy)benzene, C(38)H(68)Br(2)O(2), (III). The relative influences which halogen bonding, π-π stacking and van der Waals interactions have on these structures are analysed and the results compared with those already found for the lightest homologue, 1,2-dibromo-4,5-dimethoxybenzene, (I) [Cukiernik, Zelcer, Garland & Baggio (2008). Acta Cryst. C64, o604-o608]. The results confirm that the prevalent interactions stabilizing the structures of (II) and (III) are van der Waals contacts between the aliphatic chains. In the case of (II), weak halogen C-Br···(Br-C)' interactions are also present and contribute to the stability of the structure. In the case of (III), van der Waals interactions between the aliphatic chains are almost exclusive, weaker C-Br···π interactions being the only additional interactions detected. The results are in line with commonly accepted models concerning trends in crystal stability along a homologous series (as measured by their melting points), but the earlier report for n = 1, and the present report for n = 10 and 16, are among the few providing single-crystal information validating the hypothesis.

Br...Br and van der Waals interactions along a homologous series: crystal packing of 1,2-dibromo-4,5-dialkoxybenzenes.

The crystalline structures of four homologues of the 1,2-dibromo-4,5-dialkoxybenzene series [Br2C6H2(OCnH2n + 1)2 for n = 2, 12, 14 and 18] have been solved by means of single-crystal crystallography. Comparison along the series, including the previously reported n = 10 and n = 16 derivatives, shows a clear metric trend (b and c essentially fixed along the series and a growing linearly with n), in spite of some subtle differences in space groups and/or packing modes. A uniform packing pattern for the aliphatic chains has been found for the n = 12 to 18 homologues, which slightly differs from that of the n = 10 derivative. The crystalline structures of all the higher homologues (n = 10-18) seem to arise from van der Waals interchain interactions and, to a lesser extent, type II Br...Br interactions. The dominant role of interchain interactions provides direct structural support for the usual interpretation of melting point trends like that found along this series. Atoms in Molecules (AIM) analysis allows a comparison of the relative magnitude of the interchain and Br...Br interactions, an analysis validated by the measured melting enthalpies.