I changed my inet_interfaces setting this morning, and stopped and started 
postfix (postfix stop; postfix start)

# postconf -n inet_interfaces
inet_interfaces = 127.0.0.1, 65.121.55.42

But when I am trying to send emails to a certain company, I am getting an SPF 
error (even though my entire netblock is in the SPF settings) that claims I am 
connecting from a different IP (an IP that is assigned to the same physical 
machine as postfix) than specified in inet_interfaces.

status=bounced (host mail.synology.com[59.124.61.242] said: 550 5.7.1 
<supp...@synology.com>: Recipient address rejected: Message rejected due to: 
SPF fail - not authorized. Please see 
http://www.openspf.net/Why?s=mfrom;id=(*munged*);ip=65.121.55.45;r=supp...@synology.com
 (in reply to RCPT TO command))

covisp.net.             86400   IN      TXT     "v=spf1 mx a 
ip4:65.121.55.40/29 -all"

I know this is problem with the receiver, but I am concerned that it is 
reporting an IP that postfix shouldn't be using (.45 instead of .42).

<http://www.postfix.org/postconf.5.html#inet_interfaces>
When inet_interfaces specifies just one IPv4 and/or IPv6 address that is not a 
loopback address, the Postfix SMTP client will use this address as the IP 
source address for outbound mail. Support for IPv6 is available in Postfix 
version 2.2 and later. 



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