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With AD FS related issues, you can usually get some useful information by running the Remote Connectivity Analyser and test SSO authentications.
To run Remote Connectivity Analyser to test SSO authentication in Office 365, follow these steps:
- Open a web browser, and then browse to https://testexchangeconnectivity.com(https://testexchangeconnectivity.com/).
- Click the Office 365 tab, click Microsoft Single Sign-On, and then click Next.
- Type your user ID and the password, click to select the security acknowledgement check box, type the verification code, and then click Perform Test.
- Your user ID is your user principal name (UPN).
- You must enter actual, real credentials that are associated with the Office 365 SSO implementation that you are testing.
This normally indicates that one or more of the services on which AD FS 2.0 response relies is unavailable in some way.
How to resolve this? in my case a good old fashioned restart of the AD FS servers sorted out the problem. :)