Neat. Even knowing about niche optimization I would have guessed that you could fit 7 Options - one bit for each. But the developers were smart enough to take advantage of the fact that you can't have a Some nested below a None, so you only need to represent how many Somes there are before you reach None (or the data), allowing 254 possibilities.
I doubt they were thinking about Option<bool> when making niches work like this.
Option<NonZeroU32> seems like a much more reasonable to justify this with. Also, enums can easily have invalid bit patterns that are unused without there being any specific bit that is always available. All you need is a single variant of the enum to have a free bit, and you have a niche to shove None into.