If you put the books on the NAS then you run the risk of corruption. There are *many* threads about this, where people find that library check finds lots of errors because books are not in the proper directories. The reason: the network file protocols don't reliably support calibre's "atomic rename" methods. The result: books appear to have been lost. And yes, lots of people say "well, it works for me." I am glad they have such luck.
Bottom line: use a NAS for live calibre book storage at your own risk, and when things go south be prepared to manually reconstruct your library. Personally, I wouldn't do it because the consequences of a failure can be enormous.
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