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The Google Hangouts app allows to start a new conversation with portal users.

Overview:
+ List all users in the portal with their primary email.
+ Create a Hangout with single or multiple users.
+ Save favorite groups and load them on demand.
+ List all favorite groups that are saved along with options to View/Edit/Delete.
+ Set the number of Users and Groups per page.

You can find the full documentation of this app here:
http://wiki.rivetlogic.com/display/LRA/Google+Hangouts