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Approved/Blocked Sender List does NOT accept invalid email format. As a workaround, you may do the following:
  1. Check the email header where the email address with an invalid format is listed.
    For example:

    From: user@domain

  2. On the CAS web console > Go to Advanced Threat Protection > Exchange Online Policy > Advanced Spam Protection > Approved Header Field List > Enable the approved header field list 
  3. Add the information in the Approved Header Field List.