#1 is true regardless of the NPC/PC: a Reaction is something you do on the other fellow's turn.

#3 modified seems to be closest to the situation here: the Marilith has a reaction for/to everybody else in the fight. (But she has only one option to use, so it may not be the case that she does in fact take that reaction.)

Make a scarier Marilith: add a Reaction to take a sword-swipe at somebody.
Make it worse: proficiency in and armed with a Reach weapon.

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