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Coffee grounds are chock full of oils, acids, and other compounds. All of these chemicals, referred to collectively as "solubles," give coffee its flavor — they are what is extracted from the grounds during the brewing process.
When coffee beans are roasted, the intense heat evaporates moisture out of the heart of the bean and simultaneously draws out the volatile, oil-like substances, which then coat the outside of the bean.
This substance is not technically an oil, though. It readily evaporates after being exposed to the air, which is why the longer it sits out, the less oily it becomes.