I just got problems when upgrading to PHP 7 which may be related to this.
Until PHP 5.5 I could use "mail.domain" even if the certificate on the server was issued to the machine name. When upgrading to PHP 7 (and I guess PHP 5.6, but I cannot test it), if I don't use EXACTLY the machine name on the SMTP Host field, i get:
Warning: stream_socket_enable_crypto(): Peer certificate CN='the.machine.name' did not match expected CN='mail.domain.used' in /home/labwebdados/public_html/vinha.pt/wp-includes/class-smtp.php on line 343
I was able to replicate this on both Apache (cPanel) and nginx on PHP 7 but do not have a PHP 5.6 server to test it also.