Why is Mail asking me for the name of an smtp server for an email address that doesn't exist?

I've migrated from Snow Leopard to Mountain Lion on a new Mac, but in trying to use Mail on ML, it keeps asking me for the name of an smtp server for an email address that's never existed. The addy has my user name correct, but the server part of the address doesn't exist, or at least I've never used an email address with that provider. On ML there's no plist file for Mail, so nothing to delete there. What else can I do to get Mail working? The only other option I have is to abandon Mail as being crippled and useless, and use Postbox, which for it's price (US$9.95) is an attractive option. OTOH, I've paid for Mail after all, so it really ought to work. Any clues as to what I can do to stop its nonsensical behaviour? How do I file a bug report?
TIA.
Pauline

Amasis wrote:
On ML there's no plist file for Mail, so nothing to delete there.
~/Library/Containers/com.apple.mail/Container.plist
(Go to your Finder "Go" menu hold the option key to choose "Library", since the ~/Library is hidden on ML)

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