When I worked as a full time DoD scientist, there was a very set-in-place system for dealing with these situations, and it was normal to pay double overtime for any hours spent by an employee on after hours emergencies. This is the right way to do it. Pre-series B startups largely don't do this, but once you get to series B and C suddenly it becomes a thing because companies realize they either have to legally, or have to to prevent their employees from churning and to protect themselves from people not showing up to put out the fire.
Just do it, and do it early. Do it before Series A. That's the advice I give my consulting clients, and the approach I take with my own companies. By compensating your employees for this time you also take what would be a red flag for many would-be employees and turn it into an exciting perk.