Extrasensory. Zen Headbutt is a physical type move so therefore it is subject to Pokémon that have Static, Rough Skin, etc, but Extrasensory is special type move. They have the same power so that doesn't mean anything. Also, Zen Headbutt has an accuracy of 90 while Extrasensory has an accuracy of 100. And they both may cause flinching. So therefore extrasensory is better.
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Zen Headbutt is not a TM. It can be learned by leveling up, breeding, or by the Move Tutor.
at level 62
dragon breath safeguard luster purge zen headbutt
It knows Cross Thunder Zen Headbutt Slash Dragonbreath
I've never tried, but I DON'T Think so. Why not try it? If not, there's a man in Ilex Forrest that will gladly teach your Pokemon 'headbutt'