I think you handled it fine. Probably, nothing you say is going to make this particular person happy, because she wants everyone to revolve around her. So I would just keep politely repeating your hours and how she can get a hold of someone (else) at other times, occasionally putting it in writing with a CC to your boss as well.
This individual sounds like a pill, but generally speaking, companies have so many different policies and job categories that I wouldn't automatically understand the limitations of the person I was dealing with, especially if they ever made an exception for me (not saying you did, just in general). If I came off as clueless (hopefully not actively rude!) I hope the person would just reiterate their hours and my other options, maybe adding, "These are my hours, and I'm not able to access work data outside of them," or something like that, just to drill it in (politely).