If you set the share on the remote PC up as a mapped drive then this works fine.
There is one big caveat though - you must NEVER have both PC's running Calibre at the same time or you will corrupt your Calibre database.
The current Calibre design assumes that it has exclusive access to the database and so if two instances of Calibre are running they over-write each others changes. There is long tem work under way to redo the Calibre database layer to remove this restriction, but there is no ETA for it becoming available.
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