With the current database implementation, only one copy of Calibre can access a library at a time; all other copies of Calibre need to be shut down!
However, you can access the material stored in Calibre via the Content Server (Preferences | Sharing | Sharing over net) that will allow you to use a web browser to access the books, and then download them.
Development seems to proceeding towards a new database backend for Calibre that should allow multiple computers to run Calibre sharing a single library.
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