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Editions supported: The ability to add multiple separate domains is available in Google Apps Premier and Education Editions, and only when you are using the Next generation control panel.

When you want two names that refer to two distinct ranges of computers and users, you want two domains. When you want two names that refer to the same range of computers and users, you want two aliases for the same domain.

primary email address has a special status: it is the address the user enters to log into Google Apps, to sync with his or her mobile device, and to share Google Docs and Sites