On your iPhone 5, go to Settings>Phone>Blocked and you should see an Add New option which allows you to add a number to the block list on your iPhone. For more detailed instructions, visit: How to Block Numbers on iPhone and Find Blocked Numbers on iPhone
If you want to block a number from calling you that has called you previously, go to Phone -> Recents -> find the number you want to block and click on the little (i) symbol -> scroll to the bottom and choose Block this Caller. Alternatively go to Settings -> Phone -> Blocked and then Add New...
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