If you're not after the syntax username@domain
and really want to have [email protected]
you need to set this UPN explicitly and that differs from the SAM account name. This means that you can add a real e-mail address as login username for an AD-account.
You can also explicitly configure a user account to have a UPN whose username component is different from the SAM Account Name and whose domain component is different from the name of the domain.
The Account tab in Active Directory Users and Computers shows the UPN under the heading "User logon name" and the SAM Account Name under the heading "User logon name (pre-Windows 2000)". So if you are having trouble with particular users I would check that there aren't any discrepancies between these two values.
Reference: Any difference between DOMAIN\username and [email protected]?