Was getting the below error in one of the custom workflow activity we were using for sending email.
To fix the issue,
Login to CRM with the user selected as From.
Open Set Personal Options box
And check the check box “Allow other Microsoft Dynamics CRM users to send email on your behalf”

Hope it helps..
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Reblogged this on CRM 2015 – Sreeni Pavalla's Dynamic CRM Blog.
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