Is there a way to replace the users.xml file with and edited one?

I'd like to be able to have a collection of users.xml files with set permissions for users.

If I am deploying a new VC install, I could replace the default users.xml with my custom one, replacing all the users.

Alternatively, is it possible to insert a user's info into the users.xml i.e. if I were to add a new admin, I could create it on once VC install, then copy the relevant section and deploy it to others?

You could stop the VisualCronService and replace the users.xml. However, the optimal way is to use the API. Then you don't have to stop the service. Also, much information is encrypted in the users.xml so you can't edit it much manually.

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