Please say the Calibre has never connected to the NAS copy.
That can cause corruption. Not MIGHT, but WHEN.
As to moving (working) Libraries from one drive to another. That is correct (x)COPY using the OS. Xcopy is run from a command prompt and tends to run faster)
Rules:
1) the destination Library folder is empty (or only has the 2 original files that get overwritten)
2) Calibre (server too) is shut down
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