I don't have a problem having my Calibre library on a folder shared from an eeePC, even over my crappy (4MB/s) PLC network. I don't expect your Synology to have much problems on that side. HOWEVER.
You have to take into account that Calibre really doesn't like network outage. Like, say, if your NAS goes to sleep (or just its disks). Or your computer. Never destroyed my database, but Calibre complains of I/O failure, of course.
So, yeah. Calibre isn't really coded for it, so it's not a recommended way to do things. But as long as you're careful of always letting Calibre access its database properly, with no network outage, AND you always backup your database regularly (I do it every night), you shouldn't have a problem.
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