Calibre does not officially support network drives - so if it works for you then you are lucky! Kovid has said that there are issues with some networked filesystems around database access and locking which seems to be consistent with your symptoms.
Having said that, I run with the library on a network drive (mapped to a drive letter), but the metadata.db file held locally and that seems to be reliable and give reasonable performance. It does mean that I need to remember to sync the local metadata.db file back to the network copy of the library to keep it complete but that is easy enough to automate.
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