I think web2py is sending its mail using IPv6 because the default OS 
behavior for the environment you're using web2py on is to have your IPv6 
address as the source_address.

Can you do a test for me? In gluon/tools.py can you change: 

server = smtplib.SMTP(*smtp_args, **kwargs)

To:

server = smtplib.SMTP(*smtp_args, source_address=(YOUR_IPV4_ADDRESS, 0))

Restart web2py and tell me if this works. If it does I will make a pull 
request so you can have a mail.setttings.source_address and fix this issue 
in case something is misconfigured in your web2py environment and it's 
using IPv6 against your will.

-- 
Resources:
- http://web2py.com
- http://web2py.com/book (Documentation)
- http://github.com/web2py/web2py (Source code)
- https://code.google.com/p/web2py/issues/list (Report Issues)
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