Last time I checked, the Mame code couldn't handle 5 mouse buttons.
In mame/src/windows/input.c there's a line:
for (button = 0; button < 4; button++)
which is only looking for mouse buttons 0, 1, 2, and 3. It's quite possible that changing that 4 to a 5 would add the extra button, but I can't be certain about that without testing it.
Also, mouse buttons are a little bit more flaky than keyboard keys in Mame. For example (last I checked), you can't remap mouse buttons while a game is paused because of the way that the mouse is restricted to a single window. In addition, they're a little bit more complicated than a keyboard key because they can report "mouse button up" and "mouse button down". They typically require 3 wires instead of the usual 2.
I guess what I'm getting at is that it not be worth all the extra trouble just to squeeze a few extra buttons into your cabinet.