Step 1: In a regular hexagon, every vertex has a diametrically opposite vertex at distance \( 2a \), and two equal charges sitting at opposite vertices produce fields at the centre that are equal in magnitude and opposite in direction, so they cancel each other out.
Step 2: With six vertices, there are three such opposite pairs. Since only one vertex out of six is left empty, two of the three pairs are still complete (both charges present) and fully cancel; only the pair containing the empty vertex is incomplete.
Step 3: In that incomplete pair, the single charge present has no partner to cancel its field, so its full field of magnitude \( \frac{kq}{a^2} \) survives as the net field at the centre.
\[ \boxed{E = \dfrac{kq}{a^2}} \]