ZCS 5.0.5 Open Source on CentOS 5 upgraded from 5.0.2
I ran into the same problem with mail not being sent through the system mta at the command line or through php scripts.
/etc/postfix/main.cf did not have the correct directory for 'queue_directory'
queue_directory = /opt/zimbra/postfix/spool
should be
queue_directory = /opt/zimbra/data/postfix/spool
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