You're close; you'd want to put in slightly over 75% HP remaining. Something like 75.001 would work in theory. However, there's still some nuance. Because Substitute doesn't take exactly 25% of the user's HP, but will round down, something like 0 HP Scizor at level 100, which hits 281 stat, will make a 70 HP Substitute, which is 70/281 = ~24.91%.