E-mail server settings and credentials has to be set seperatly in the purechat.config.
Why not use the basic mailSettings in the web.config of the web site ?
Ex.:
<system.net>
<!--Mail settings -->
<mailSettings>
<!--
<smtp deliveryMethod="Network">
<network host="localhost" port="25" defaultCredentials="true"/>
</smtp>
-->
<smtp deliveryMethod="SpecifiedPickupDirectory">
<specifiedPickupDirectory pickupDirectoryLocation="C:\Inetpub\mailroot\Drop\" />
</smtp>
</mailSettings>
</system.net>
That way there is only one place to maintain these settings, and you have more features, like specifiedPickupDirectory for testing purposes.