The first reported structure of a pyridin-2-ylboron derivative, viz. the title compound, C(11)H(15)BBrNO(2), (I), is compared with its regioisomer 2-bromo-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine, (II) [Sopková-de Oliveira Santos, Lancelot, Bouillon & Rault (2003). Acta Cryst. C59, o111-o113]. Structural differences are observed, firstly in the orientation of the dioxaborolane ring with respect to the pyridine ring and secondly in the bond angles of the BO(2) group. These differences do not explain the experimentally observed differences in chemical reactivity between (I) and (II) but do confirm the relatively lower stability of (I). However, ab initio calculations of the HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital), based on the known crystal structures of the two compounds, show different distributions, which correspond to the differences observed during chemical reactions.