I think the problem is the you have to add the senders in the accepted IP list
webmail doesn't give a problem, because you send the mail from the mailserver itself.
When you send it from outlook, your client IP has to authenticate with the mailserver and that is where it should be allowed to send email.
The actual setting would be here (in my 5.0.18 FOSS )
Configuration --> servers --> your server name --> MTA (tab)
MTA Trusted Networks
Hope it helps
