This is mentioned in a number of threads. It is a very good way to corrupt your data. Currently Calibre is intended for single access only and use on an NAS is not recommended. I also have my Calibre Database on an NAS and it works well. However, I am careful to limit access to single access and keep a recent backup of the whole library on another machine. I have had to rebuild the database once after accidental concurrent access.
I recall at one stage Kovid, the developer of Calibre, was working on a different database backend but I'm not sure if there are currently any plans to support concurrent access. At the moment concurrent access is just asking for corruption problems.
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