Adding up the list of mailboxes will never equal the size of the store. There are various reasons for that, the main one being that ESM doesn't show you everything.
"When you view the space that a mailbox uses in Exchange System Manager, the amount only includes the space that is used by the Priv.edb file. The amount does not include the space that the Priv.stm file uses. "
http://support.microsoft.com/kb/828070/Due to the way that the database size limit is imposed, an offline defrag is a waste of time. The limit is imposed by taking the physical size minus the amount of white space. You can see the amount of white space in event ID 1221.
As such, doing an offline defrag doesn't gain you anything because you are gaining space that is already available to you.
However if you have been deleting data then it may well be stored in deleted item retention. You would need to reduce the DIR time to release that space quicker.
Simon.