Zen Cart will use the port setting shown in Admin->Configuration->Email Options->SMTP port
That's the only port it will use for SMTP email delivery. The port number will not be found in any "file". If it's updating, then you will see it on that screen.
If you're getting "Could not connect to SMTP host" errors, then that means Zen Cart is unable to make an SMTP connection using the SMTP host+port+username+password.
That could be a result of firewall issues on either server, errors in the settings you supplied, or restrictions imposed from within the SMTP server itself.


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