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I don't know exactly the path (it deppends on the OS). In the desktop/laptop installation, you can open the folder from the user interface and you see the path (I don't know the option by heart and I don't have calibre here). In the portable installation: Calibre Portable/Calibre Settings.
You only need to synchronize these two folders (and subfolders). I would recommend not to synchronize the gui.json file.
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