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SQLite is probably unhappy. If you are using windows (although it appears that you are not), Calibre tends not to like UNC paths. If you are using them, mount the NAS volume as a drive and use drive letters. Another problem that people have run into is that some NAS don't do locking in a reasonable way. Can't speak for yours.
As for regenerating the metadata, no, not on the release you are probably running. And in any event, if copying the database to the NAS doesn't work, then almost certainly rebuilding the database on the NAS won't work.
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