You can't, the XP Restore facility is only useful if you have a working (or at least half working messed up) machine. If the Pc is locked up/frozen or won't boot you can't use it. That's why other forms of backing files up are highly recommened.
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Synology invites you to visit them at Insomnia on 26th – 29th August. Book your tickets now and visit Synology.