OK, figured out the issue and it seems to be a weird permissions issue I was having, where Calibre was creating a folder but the umask was too restrictive to allow the creation of files properly. No idea why it appeared to be fixed after a reboot, but added new umask to the service and it is all right as rain now.
As a side note, it works when you specify either the library location or the URL now.
Cheers for the help mate!
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