For GMail and Hotmail accounts, sending emails is throttled so as not to trigger the spam guard of the server. That's why you're seeing the five minute delay.
The SMTP server is the server that sends the mail from your Googlemail account to your Kindle address. The username for the server must include the @gmail.com or @googlemail.com part of your address (in fact, the name should be your complete GMail address).
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