I believe it will be contacting "outlook.office365.com"
This is the latest list as of 27/05
Article Here: Office 365 URLs and IP address ranges
For what it's worth, you might want to look at password sync as an alternative to ADFS if you're not getting the scenario you want. Maintaining a reliable and robust ADFS infrastructure when it's not delivering SSO 100% of the time could be overkill, whereas password sync gives you "consistent" sign-on which doesn't need you to have highly available servers.
(I know I've linked to this many times in various threads, but it's still pretty accurate: Deploying Office 365 Education? You don't need single sign-on, and here's why!)
I feel this post is better here, rather than start a new topic, but has anyone managed to set this up as part of an admin file for Office 2013? I.e. Can we set up a basic profile for Outlook 2013 to ease our students connecting to O365? We're likely to be deploying Win8.1 with Office 2013 and I'd like to give a helping 'nudge' where possible.
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