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Needs more details. Paste the full error message. Right now, I'm guessing that this happens when you click the test button in the email preferences dialog? Did you set up your GMail account correctly (as in "clicked the button the dialog provides")?
The error message seems to indicate that Calibre cannot communicate to the GMail server, because the connection was refused. This could be because you used the wrong port, or because your firewall blocked it, or because the server address is wrong, or any number of other reasons.
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