I had an issue in SSRS where user configured subscriptions would always fail to find their email address (an email server configuration problem probably).
My work-around was to allow users to type in (or paste in) their full email addresses.
To do this I first created a copy of the reporting services configuration file “c:\ Microsoft SQL Server\ MSRS11.MSSQLSERVER\ Reporting Services\ ReportServer\ rsreportserver.config”.
Then edited the original in two places …
1) I changed [SendEmailToUserAlias]True[/SendEmailToUserAlias] to False.
2) Then I inserted the name of the SMTP Server into the middle of [DefaultHostName][/DefaultHostName].
NOTE: To find the name of the SMTP Server I opened Reporting Services Configuration Manager, and navigated to “E-Mail Settings”.