There are three places you need to check:
1. The company hours
2. The user's hours
3. Check for any Advanced Calling Rules which would stop them from receiving calls during that time period.
You indicate that the hours are set from 7am to 2pm but you don't elaborate as to whether these are company hours or user hours. If the company hours and user hours are all set correcty, my guess is that there is an Advanced Calling Rule in place somewhere.