I am not 100% sure. But I will lay out some possibilities. First of all, app.config is not the correct name for the file. Although this is app.config in your project, it is automatically renamed to binary.exe.config or binary.dll.config (depending on the type of project), where the binary name is the name of the project.
Secondly, I am not 100% sure if the dll.config files always load correctly and read .NET when the application loads. I do not think that this happens automatically, and that there is an additional call that you must make to read the configuration file, if it is for dll. If you create a configuration file in accordance with your exe, it will download and be available to you.
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