If someone is suspected of a crime, and the police are investigating said person, but haven't made an arrest, just questioned a suspect, and another person said that if arrested, they'll take the blame for the suspected guilty person, what would happen to both parties.
What do you mean "what happens"? An innocent person can't take the blame. You can't just pick up the tab for another person's crime. If discovered, both would suffer legal consequences. Also, the detectives are only interested in catching the right person, they will not be satisfied with and stop at a mere confession.
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