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My first reaction would be to wonder why a User with Windows 7 in its /User path is being pointed at when you now, as I understand it to be, have a Windows 8 PC?
If something is incorrect there then a permission problem would result. Windows 8 installs over Windows 7, in my experience, always create a new clean User path.
This may have come about, for example, if you have pointed Calibre to a backup User folder, archiving the old Windows 7 user account, that was created by the Windows 8 install.
If looking at the User folders does not produce an obvious answer to that as to a problem or not, then a test would be to create a new user account and install Calibre with that account and see what happens.
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