Can i center my steering wheel with this bolt?

Got an alignment last last saturday (not CanAlignment), not sure if they botched the job, but my wheel is now pointing to the right. If I unscrew this bolt, would I be able to turn the hub, or does this fuck something up?

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Go back. Tell them to straighten your wheel. You can do it with that, but they fucked up. Part of a proper alignment is to make sure the wheel is straight at the end of it. They should fix it free of charge.