It is not intended for this.
You can use the System.Configuration.ConfigurationSettings classes to explicitly open the file in code to read your settings. This will work, but the designer will not give you any help in creating your settings files.
Do you have a problem with class settings?
Another way that can help you is to create a custom configuration section that you can put in a file. You can then split each of your settings into your own configuration section. Can this satisfy your goals?
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