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In a small bowl, combine brown sugar, ground coffee, paprika, garlic powder, pepper and salt. Trim fat from brisket. Rub mixture over all surfaces of the brisket.
If necessary, cut meat to fit into a 3-1/2- or 4-quart slow cooker. Place meat in cooker. Place onion slices over brisket. Combine coffee and vinegar, pour over onions.
Cover and cook on Low for 9 to 10 hours or on High for 4 1/2 to 5 hours. Transfer meat to a cutting board. Slice meat across the grain. With a slotted spoon, remove the onions from the cooking liquid. Serve with meat.