Well, given that I have always had a customer service bias to any position I've held, I feel you have to draw a fuzzy line.
Data entry may not be your responsibility, but it could very well be your job to make that position as efficient as possible.
IT penetrates all the other departments, even Sanitation. The CIO or the manager should be working at a level to know the users' and customers' needs and you should feed them information about what options they have to exercise.
If you draw a clear line in the sand and say "This is that for which we are responsible" be sure to draw a wavy line beyond that and say, "But we understand that we may be able to help and assist up to this point."
This allows you to introduce the idea of priorities. For instance, [and this can vary wildly depending on the ultimate cause for your organization] which is more important: general internet access, or the monitor working for a data entry grunt in accounting?
As the database admin, I'm surprised you're tasked with the CIO's job.