MailEnable only provides one SMTP connector service and cannot be configured using multiple connectors. To send all outgoing mail via an external mail server you would need to configure the MailEnable SMTP service to smart host. You can find the SMTP smart host option under the SMTP properties window.
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To have MailEnable relay email through Pepipost, follow the below steps:
Open the MailEnable Admin application.
Expand the Servers tab in the left-hand navigation pane. Click localhost > System > Right click on SMTP
Once you are in the SMTP Properties box click on the Smart Host tab.
Check the box next to Smart Host Enabled.
Under IP/Domain type: smtp.pepipost.com. In the Port field type: 25 or 587 or 2525 (depending upon which port is opened at your end).
Check the box that says ‘The remote server requires authentication’
Enter your Pepipost username and password and click Apply.
Go to Windows Services and restart MailEnable