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Possible
Calibre is transactional,
any network delays can corrupt the sync between the what the DB part has and what the (book) file IS.
Some folk get away doing this on a NAS.
Some keep the DB local and just the book folders on the NAS
Personally, I just cloned my existing drive onto a bigger HD, and put it in my PC
Many mid-tower PC's can hold a second drive inside. Some have an external eSATA port, so speed does not suffer
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